Methods for manufacturing biocompatible cathode slurry for use in biocompatible batteries

ABSTRACT

Methods and apparatus to form biocompatible energization elements are described. In some examples, the methods and apparatus to form the biocompatible energization elements involve forming cavities comprising active cathode chemistry. The active elements of the cathode and anode are sealed with a biocompatible material. In some examples, a field of use for the methods and apparatus may include any biocompatible device or product that requires energization elements.

CROSS REFERENCE TO RELATED APPLICATIONS

This patent application claims the benefit of U.S. ProvisionalApplication No. 62/040,178 filed Aug. 21, 2014.

BACKGROUND OF THE INVENTION

1. Field of the Invention

Methods for manufacturing biocompatible cathode slurry for use inbiocompatible batteries are described. In some examples, the methodsinvolve manufacturing an electrical conductor through which an electriccurrent enters or leaves a vacuum or fluent. In some examples, a fieldof use for the methods for manufacturing biocompatible cathode slurryfor use in biocompatible batteries may include any biocompatible deviceor product that requires energy.

2. Discussion of the Related Art

Recently, the number of medical devices and their functionality hasbegun to rapidly develop. These medical devices may include, forexample, implantable pacemakers, electronic pills for monitoring and/ortesting a biological function, surgical devices with active components,contact lenses, infusion pumps, and neurostimulators. Addedfunctionality and an increase in performance to many of theaforementioned medical devices has been theorized and developed.However, to achieve the theorized added functionality, many of thesedevices now require self-contained energization means that arecompatible with the size and shape requirements of these devices, aswell as the energy requirements of the new energized components.

Some medical devices may include electrical components such assemiconductor devices that perform a variety of functions and may beincorporated into many biocompatible and/or implantable devices.However, such semiconductor components require energy and, thus,energization elements should preferably also be included in suchbiocompatible devices. The topology and relatively small size of thebiocompatible devices may create challenging environments for thedefinition of various functionalities. In many examples, it may beimportant to provide safe, reliable, compact and cost effective means toenergize the semiconductor components within the biocompatible devices.Therefore, a need exists for biocompatible energization elements formedfor implantation within or upon biocompatible devices where thestructure of the millimeter or smaller sized energization elementsprovides enhanced function for the energization element whilemaintaining biocompatibility.

One such energization element used to power a device may be a battery. Acommon element in batteries that may contain various types of chemicalbased energy storage materials is the battery cathode. The function ofbatteries may depend critically on the design of structure, materials,and processes related to the formation of the battery cathode.Furthermore, in some examples, the containment of battery cathodematerials may be an important aspect of biocompatibility.

Cathode slurry may be a component of the biocompatible battery. Thechoice of cathode slurry may have an effect on integration,manufacturing, logistics, reliability, and yield of the biocompatiblebattery. Slurry technology has evolved to keep pace with the demandingrequirements of the slurry industry. Cathode slurry manufacturing mayrequire expertise in the areas of particle synthesis; dispersion,mixing, and filtration; electrochemistry, colloid science and surfacechemistry; fluid dynamics; and numerical analysis. Operations expertisemay be useful for a supplier to flawlessly manufacture a cathode slurryday in and day out, and deliver the cathode slurry for high volumemanufacturing. In addition, when designing battery elements and themanufacturing systems used to make them as biocompatible energy sourcesfor ophthalmic devices, expertise in ophthalmics and ophthalmic devicesmay be important for the safety profile of biocompatible devices formedusing the cathode slurry. Therefore a need exists for novel examples ofmanufacturing small biocompatible cathodes for use in biocompatibleenergization elements.

SUMMARY OF THE INVENTION

One general aspect of the present invention includes a method formanufacturing a cathode slurry for use in a biocompatible battery. Thismethod may include the steps of mixing one or more of a liquid phasepre-mixture with one or more of a solid phase pre-mixture into a cathodeslurry mixture. Then, obtain a laminar structure where the laminarstructure has a volume removed to form a cavity. Next, filter thecathode slurry mixture. Finally, distribute the cathode slurry mixtureinto the cavity of the laminar structure to form a biocompatible cathodefor use in a biocompatible battery.

Implementations may include one or more of the following features. Themethod including checking a quality of the solid phase pre-mixture andthe liquid phase pre-mixture. The method may also include storing andrecirculating the cathode slurry mixture after filtering the cathodeslurry mixture. The method may also include drying the cathode slurrymixture. The liquid phase pre-mixture may include of one or morereagents where at least one reagent is a liquid phase reagent. Themethod may also include filtering the liquid phase reagents. One liquidphase reagent may include a solvent. The solvent may include toluene.

The solid phase pre-mixture may include of one or more solid phasereagents. The method may also include sieving the solid phase reagentsto a uniform particle size. The method may also include solid phasereagents including a hydrophilic binder. The method may also include onesolid phase pre-mixture including a transition metal oxide. Thetransition metal oxide may include manganese dioxide. The method mayalso include one solid phase reagent including a carbon allotrope. Thecarbon allotrope may include graphite. The graphite may include carbonblack. The method may also include one solid phase reagent including ahydrophobic binder. The hydrophobic binder may include polyisobutylene(PIB). The hydrophobic binder may include a fluorocarbon solid. Thefluorocarbon solid may include polytetrafluoroethylene (PTFE). Themethod may also include a biomedical device which is a contact lens.

One general aspect of the present invention includes a method formanufacturing a biocompatible cathode for use in a biocompatible batteryincluding the steps of: obtaining toluene, manganese dioxide, carbonblack, and polyisobutylene. The method may also include filteringtoluene. The method may also include sieving manganese dioxide, carbonblack, and polyisobutylene. The method may also include mixing thetoluene and the polyisobutylene into a liquid phase pre-mixture. Themethod may also include mixing the manganese dioxide and carbon blackinto a solid phase pre-mixture. The method may also include checking aquality of both the solid and liquid phase pre-mixtures. The method mayalso include mixing the solid phase pre-mixture and liquid phasepre-mixture into a cathode slurry mixture then filtering the cathodeslurry mixture. The method may also include storing the cathode slurrymixture then recirculating the cathode slurry mixture. The method mayalso include obtaining a laminar structure where the laminar structurehas a volume removed to form a cavity. The method may also includefiltering the stored cathode slurry mixture then distributing thefiltered cathode slurry mixture into the cavity of the laminarstructure, followed by drying the cathode slurry mixture to form abiocompatible cathode for use in a biocompatible battery.

One general aspect of the present invention includes a method formanufacturing a cathode slurry for use in a biomedical device includingthe steps of: mixing one or more of a liquid phase pre-mixture with oneor more of a solid phase pre-mixture into a cathode slurry mixture,obtaining a laminar structure where the laminar structure has a volumeremoved to form a cavity, and filtering the cathode slurry mixture. Themethod may also include distributing the cathode slurry mixture into thecavity of the laminar structure forming the cathode slurry for use in abiomedical device, where the biomedical device includes an insertdevice. The insert device may include an electroactive elementresponsive to a controlling voltage signal. The method may also includea biocompatible battery. The biocompatible battery may include a firstand second electrode, an anode, a separator, a laminar structure (whereat least one layer of the laminar structure has a volume removed to forma cavity). The method may also include the cathode slurry where at leastan average molecular size of one component of the cathode slurry isreduced in particle size by milling that component. The method may alsoinclude the cathode slurry capable of filling the cavity, based on itsrheology, while maintaining electro-conductivity through the laminarstructure in the cavity. The method may also include a circuitelectrically connected to a biocompatible battery, where the circuitprovides the controlling voltage signal. The method may include abiomedical device that is a contact lens.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A-1D illustrate exemplary aspects of biocompatible energizationelements in concert with the exemplary application of contact lenses.

FIG. 2 illustrates the exemplary size and shape of individual cells ofan exemplary battery design.

FIG. 3A illustrates a first stand-alone, packaged biocompatibleenergization element with exemplary anode and cathode connections.

FIG. 3B illustrates a second stand-alone, packaged biocompatibleenergization element with exemplary anode and cathode connections.

FIGS. 4A-4N illustrate exemplary method steps for the formation ofbiocompatible energization elements for biomedical devices.

FIG. 5 illustrates an exemplary fully formed biocompatible energizationelement.

FIGS. 6A-6F illustrate exemplary method steps for structural formationof biocompatible energization elements.

FIGS. 7A-7F illustrate exemplary method steps for structural formationof biocompatible energization elements utilizing an alternateelectroplating method.

FIGS. 8A-8H illustrate exemplary method steps for the formation ofbiocompatible energization elements with hydrogel separator forbiomedical devices.

FIGS. 9A-C illustrate exemplary methods steps for the structuralformation of biocompatible energization elements utilizing alternativehydrogel processing examples.

FIGS. 10A-10F illustrate optimized and non-optimized depositing of acathode mixture into a cavity.

FIG. 11 illustrates agglomeration of a cathode mixture inside of acavity.

FIG. 12 illustrates exemplary method steps for manufacturingbiocompatible cathode slurry for use in biocompatible batteries.

DETAILED DESCRIPTION OF THE INVENTION

Methods of manufacturing biocompatible cathode slurry for use inbiocompatible batteries are disclosed in this application. In thefollowing sections, detailed descriptions of various examples aredescribed. The descriptions of examples are exemplary embodiments only,and various modifications and alterations may be apparent to thoseskilled in the art. Therefore, the examples do not limit the scope ofthis application. The cathode mixtures, and the structures that containthem, may be designed for use in biocompatible batteries. In someexamples, these biocompatible batteries may be designed for use in, orproximate to, the body of a living organism.

GLOSSARY

In the description and claims below, various terms may be used for whichthe following definitions will apply:

“Anode” as used herein refers to an electrode through which electriccurrent flows into a polarized electrical device. The direction ofelectric current is typically opposite to the direction of electronflow. In other words, the electrons flow from the anode into, forexample, an electrical circuit.

“Binder” as used herein refers to a polymer that is capable ofexhibiting elastic responses to mechanical deformations and that ischemically compatible with other energization element components. Forexample, binders may include electroactive materials, electrolytes,polymers, etc.

“Biocompatible” as used herein refers to a material or device thatperforms with an appropriate host response in a specific application.For example, a biocompatible device does not have toxic or injuriouseffects on biological systems.

“Cathode” as used herein refers to an electrode through which electriccurrent flows out of a polarized electrical device. The direction ofelectric current is typically opposite to the direction of electronflow. Therefore, the electrons flow into the cathode of the polarizedelectrical device, and out of, for example, the connected electricalcircuit.

“Coating” as used herein refers to a deposit of material in thin forms.In some uses, the term will refer to a thin deposit that substantiallycovers the surface of a substrate it is formed upon. In other morespecialized uses, the term may be used to describe small thin depositsin smaller regions of the surface.

“Electrode” as used herein may refer to an active mass in the energysource. For example, it may include one or both of the anode andcathode.

“Energized” as used herein refers to the state of being able to supplyelectrical current or to have electrical energy stored within.

“Energy” as used herein refers to the capacity of a physical system todo work. Many uses of the energization elements may relate to thecapacity of being able to perform electrical actions.

“Energy Source” or “Energization Element” or “Energization Device” asused herein refers to any device or layer which is capable of supplyingenergy or placing a logical or electrical device in an energized state.The energization elements may include batteries. The batteries may beformed from alkaline type cell chemistry and may be solid-statebatteries or wet cell batteries.

“Fillers” as used herein refer to one or more energization elementseparators that do not react with either acid or alkaline electrolytes.Generally, fillers may include substantially water insoluble materialssuch as carbon black; coal dust; graphite; metal oxides and hydroxidessuch as those of silicon, aluminum, calcium, magnesium, barium,titanium, iron, zinc, and tin; metal carbonates such as those of calciumand magnesium; minerals such as mica, montmorollonite, kaolinite,attapulgite, and talc; synthetic and natural zeolites such as Portlandcement; precipitated metal silicates such as calcium silicate; hollow orsolid polymer or glass microspheres, flakes and fibers; etc.

“Functionalized” as used herein refers to making a layer or device ableto perform a function including, for example, energization, activation,and/or control.

“Mold” as used herein refers to a rigid or semi-rigid object that may beused to form three-dimensional objects from uncured formulations. Someexemplary molds include two mold parts that, when opposed to oneanother, define the structure of a three-dimensional object.

“Power” as used herein refers to work done or energy transferred perunit of time.

“Rechargeable” or “Re-energizable” as used herein refer to a capabilityof being restored to a state with higher capacity to do work. Many usesmay relate to the capability of being restored with the ability to flowelectrical current at a certain rate for certain, reestablished timeperiods.

“Reenergize” or “Recharge” as used herein refer to restoring to a statewith higher capacity to do work. Many uses may relate to restoring adevice to the capability to flow electrical current at a certain ratefor a certain reestablished time period.

“Released” as used herein and sometimes referred to as “released from amold” means that a three-dimensional object is either completelyseparated from the mold, or is only loosely attached to the mold, sothat it may be removed with mild agitation.

“Stacked” as used herein means to place at least two component layers inproximity to each other such that at least a portion of one surface ofone of the layers contacts a first surface of a second layer. In someexamples, a coating, whether for adhesion or other functions, may residebetween the two layers that are in contact with each other through saidcoating.

“Traces” as used herein refer to energization element components capableof connecting together the circuit components. For example, circuittraces may include copper or gold when the substrate is a printedcircuit board and may typically be copper, gold or printed film in aflexible circuit. A special type of “Trace” is the current collector.Current collectors are traces with electrochemical compatibility thatmake the current collectors suitable for use in conducting electrons toand from an anode or cathode in the presence of electrolyte.

The methods and apparatus presented herein relate to formingbiocompatible energization elements for inclusion within or on flat orthree-dimensional biocompatible devices. A particular class ofenergization elements may be batteries that are fabricated in layers.The layers may also be classified as laminate layers. A battery formedin this manner may be classified as a laminar battery.

There may be other examples of how to assemble and configure batteriesaccording to the present invention, and some may be described infollowing sections. However, for many of these examples, there areselected parameters and characteristics of the batteries that may bedescribed in their own right. In the following sections, somecharacteristics and parameters will be focused upon.

Exemplary Biomedical Device Construction with Biocompatible EnergizationElements

An example of a biomedical device that may incorporate the EnergizationElements, batteries, of the present invention may be an electroactivefocal-adjusting contact lens. Referring to FIG. 1A, an example of such acontact lens insert may be depicted as contact lens insert 100. In thecontact lens insert 100, there may be an electroactive element 120 thatmay accommodate focal characteristic changes in response to controllingvoltages. A circuit 105, to provide those controlling voltage signals aswell as to provide other functions such as controlling sensing of theenvironment for external control signals, may be powered by abiocompatible battery element 110. As depicted in FIG. 1A, the batteryelement 110 may be found as multiple major pieces, in this case threepieces, and may include the various configurations of battery chemistryelements as has been discussed. The battery element 110 may have variousinterconnect features to join together pieces as may be depictedunderlying the region of interconnect 114. The battery element 110 maybe connected to a circuit element that may have its own substrate 111upon which interconnect features 125 may be located. The circuit 105,which may be in the form of an integrated circuit, may be electricallyand physically connected to the substrate 111 and its interconnectfeatures 125.

Referring to FIG. 1B, a cross sectional relief of a contact lens 150 maycomprise contact lens insert 100 and its discussed constituents. Thecontact lens insert 100 may be encapsulated into a skirt of contact lenshydrogel 155 which may encapsulate the contact lens insert 100 andprovide a comfortable interface of the contact lens 150 to a user's eye.

In reference to concepts of the present invention, the battery elementsmay be formed in a two-dimensional form as depicted in FIG. 1C. In thisdepiction there may be two main regions of battery cells in the regionsof battery component 165 and the second battery component in the regionof battery chemistry element 160. The battery elements, which aredepicted in flat form in FIG. 1C, may connect to a circuit element 163,which in the example of FIG. 1C may comprise two major circuit areas167. The circuit element 163 may connect to the battery element at anelectrical contact 161 and a physical contact 162. The flat structuremay be folded into a three-dimensional conical structure as has beendescribed with respect to the present invention. In that process asecond electrical contact 166 and a second physical contact 164 may beused to connect and physically stabilize the three-dimensionalstructure. Referring to FIG. 1D, a representation of thisthree-dimensional conical structure 180 may be found. The physical andelectrical contact points 181 may also be found and the illustration maybe viewed as a three-dimensional view of the resulting structure. Thisstructure may include the modular electrical and battery component thatwill be incorporated with a lens insert into a biocompatible device.

Segmented Battery Schemes

Referring to FIG. 2, an example of different types of segmented batteryschemes is depicted for an exemplary battery element for a contact lenstype example. The segmented components may be relatively circular-shaped271, square-shaped 272 or rectangular-shaped. In rectangular-shapedexamples, the rectangles may be small rectangular shapes 273, largerrectangular shapes 274, or even larger rectangular shapes 275.

Custom Shapes of Flat Battery Elements

In some examples of biocompatible batteries, the batteries may be formedas flat elements. Referring to FIG. 3A, an example of a rectangularoutline 310 of the battery element may be depicted with an anodeconnection 311 and a cathode connection 312. Referring to FIG. 3B, anexample of a circular outline 330 of a battery element may be depictedwith an anode connection 331 and a cathode connection 332.

In some examples of flat-formed batteries, the outlines of the batteryform may be dimensionally and geometrically configured to fit in customproducts. In addition to examples with rectangular or circular outlines,custom “free-form” or “free shape” outlines may be formed which mayallow the battery configuration to be optimized to fit within a givenproduct.

In the exemplary biomedical device case of a variable optic, a“free-form” example of a flat outline may be arcuate in form. The freeform may be of such geometry that when formed to a three-dimensionalshape, it may take the form of a conical, annular skirt that fits withinthe constraining confines of a contact lens. It may be clear thatsimilar beneficial geometries may be formed where medical devices haverestrictive 2D or 3D shape requirements.

Biocompatibility Aspects of Batteries

As an example, the batteries according to the present invention may haveimportant aspects relating to safety and biocompatibility. In someexamples, batteries for biomedical devices may need to meet requirementsabove and beyond those for typical usage scenarios. In some examples,design aspects may be considered related to stressing events. Forexample, the safety of an electronic contact lens may need to beconsidered in the event a user breaks the lens during insertion orremoval. In another example, design aspects may consider the potentialfor a user to be struck in the eye by a foreign object. Still furtherexamples of stressful conditions that may be considered in developingdesign parameters and constraints may relate to the potential for a userto wear the lens in challenging environments like the environment underwater or the environment at high altitude in non-limiting examples.

The safety of such a device may be influenced by the materials that thedevice is formed with or from, by the quantities of those materialsemployed in manufacturing the device, and also by the packaging appliedto separate the devices from the surrounding on- or in-body environment.In an example, pacemakers may be a typical type of biomedical devicewhich may include a battery and which may be implanted in a user for anextended period of time. Accordingly, in some examples, such pacemakersmay typically be packaged with welded, hermetic titanium enclosures, orin other examples, multiple layers of encapsulation. Emerging poweredbiomedical devices may present new challenges for packaging, especiallybattery packaging. These new devices may be much smaller than existingbiomedical devices, for example, an electronic contact lens or pillcamera may be significantly smaller than a pacemaker. In such examples,the volume and area available for packaging may be greatly reduced.

Electrical Requirements of Microbatteries

Another area for design considerations may relate to electricalrequirements of the device, which may be provided by the battery. Inorder to function as a power source for a medical device, an appropriatebattery may need to meet the full electrical requirements of the systemwhen operating in a non-connected or non-externally powered mode. Anemerging field of non-connected or non-externally powered biomedicaldevices may include, for example, vision-correcting contact lenses,health monitoring devices, pill cameras, and novelty devices. Recentdevelopments in integrated circuit (IC) technology may permit meaningfulelectrical operation at very low current levels, for example, picoampsof standby current and microamps of operating current. Integratedcircuits may also permit very small devices.

Microbatteries for biomedical applications may be required to meet manysimultaneous, challenging requirements. For example, the microbatterymay be required to have the capability to deliver a suitable operatingvoltage to an incorporated electrical circuit. This operating voltagemay be influenced by several factors including the IC process “node,”the output voltage from the circuit to another device, and a particularcurrent consumption target which may also relate to a desired devicelifetime.

With respect to the IC process, nodes may typically be differentiated bythe minimum feature size of a transistor, such as its “so-called”transistor channel. This physical feature, along with other parametersof the IC fabrication, such as gate oxide thickness, may be associatedwith a resulting rating standard for “turn-on” or “threshold” voltagesof field-effect transistors (FET's) fabricated in the given processnode. For example, in a node with a minimum feature size of 0.5 microns,it may be common to find FET's with turn-on voltages of 5.0V. However,at a minimum feature size of 90 nm, the FET's may turn-on at 1.2, 1.8,and 2.5V. The IC foundry may supply standard cells of digital blocks,for example, inverters and flip-flops that have been characterized andare rated for use over certain voltage ranges. Designers chose an ICprocess node based on several factors including density of digitaldevices, analog/digital mixed signal devices, leakage current, wiringlayers, and availability of specialty devices such as high-voltageFET's. Given these parametric aspects of the electrical components,which may draw power from a microbattery, it may be important for themicrobattery power source to be matched to the requirements of thechosen process node and IC design, especially in terms of availablevoltage and current.

In some examples, an electrical circuit powered by a microbattery, mayconnect to another device. In non-limiting examples, themicrobattery-powered electrical circuit may connect to an actuator or atransducer. Depending on the application, these may include alight-emitting diode (LED), a sensor, a microelectromechanical system(MEMS) pump, or numerous other such devices. In some examples, suchconnected devices may require higher operating voltage conditions thancommon IC process nodes. For example, a variable-focus lens may require35V to activate. The operating voltage provided by the battery maytherefore be a critical consideration when designing such a system. Insome examples of this type of consideration, the efficiency of a lensdriver to produce 35V from a 1V battery may be significantly less thanit might be when operating from a 2V battery. Further requirements, suchas die size, may be dramatically different considering the operatingparameters of the microbattery as well.

Individual battery cells may typically be rated with open-circuit,loaded, and cutoff voltages. The open-circuit voltage is the potentialproduced by the battery cell with infinite load resistance. The loadedvoltage is the potential produced by the cell with an appropriate, andtypically also specified, load impedance placed across the cellterminals. The cutoff voltage is typically a voltage at which most ofthe battery has been discharged. The cutoff voltage may represent avoltage, or degree of discharge, below which the battery should not bedischarged to avoid deleterious effects such as excessive gassing. Thecutoff voltage may typically be influenced by the circuit to which thebattery is connected, not just the battery itself, for example, theminimum operating voltage of the electronic circuit. In one example, analkaline cell may have an open-circuit voltage of 1.6V, a loaded voltagein the range 1.0 to 1.5V, and a cutoff voltage of 1.0V. The voltage of agiven microbattery cell design may depend upon other factors of the cellchemistry employed. And, different cell chemistry may therefore havedifferent cell voltages.

Cells may be connected in series to increase voltage; however, thiscombination may come with tradeoffs to size, internal resistance, andbattery complexity. Cells may also be combined in parallelconfigurations to decrease resistance and increase capacity; however,such a combination may tradeoff size and shelf life.

Battery capacity may be the ability of a battery to deliver current, ordo work, for a period of time. Battery capacity may typically bespecified in units such as microamp-hours. A battery that may deliver 1microamp of current for 1 hour has 1 microamp-hour of capacity. Capacitymay typically be increased by increasing the mass (and hence volume) ofreactants within a battery device; however, it may be appreciated thatbiomedical devices may be significantly constrained on available volume.Battery capacity may also be influenced by electrode and electrolytematerial.

Depending on the requirements of the circuitry to which the battery isconnected, a battery may be required to source current over a range ofvalues. During storage prior to active use, a leakage current on theorder of picoamps to nanoamps may flow through circuits, interconnects,and insulators. During active operation, circuitry may consume quiescentcurrent to sample sensors, run timers, and perform such low powerconsumption functions. Quiescent current consumption may be on the orderof nanoamps to milliamps. Circuitry may also have even higher peakcurrent demands, for example, when writing flash memory or communicatingover radio frequency (RF). This peak current may extend to tens ofmilliamps or more. The resistance and impedance of a microbattery devicemay also be important to design considerations.

Shelf life typically refers to the period of time which a battery maysurvive in storage and still maintain useful operating parameters. Shelflife may be particularly important for biomedical devices for severalreasons. Electronic devices may displace non-powered devices, as forexample may be the case for the introduction of an electronic contactlens. Products in these existing market spaces may have establishedshelf life requirements, for example, three years, due to customer,supply chain, and other requirements. It may typically be desired thatsuch specifications not be altered for new products. Shelf liferequirements may also be set by the distribution, inventory, and usemethods of a device including a microbattery. Accordingly,microbatteries for biomedical devices may have specific shelf liferequirements, which may be, for example, measured in the number ofyears.

In some examples, three-dimensional biocompatible energization elementsmay be rechargeable. For example, an inductive coil may also befabricated on the three-dimensional surface. The inductive coil couldthen be energized with a radio-frequency (“RF”) fob. The inductive coilmay be connected to the three-dimensional biocompatible energizationelement to recharge the energization element when RF is applied to theinductive coil. In another example, photovoltaics may also be fabricatedon the three-dimensional surface and connected to the three-dimensionalbiocompatible energization element. When exposed to light or photons,the photovoltaics will produce electrons to recharge the energizationelement.

In some examples, a battery may function to provide the electricalenergy for an electrical system. In these examples, the battery may beelectrically connected to the circuit of the electrical system. Theconnections between a circuit and a battery may be classified asinterconnects. These interconnects may become increasingly challengingfor biomedical microbatteries due to several factors. In some examples,powered biomedical devices may be very small thus allowing little areaand volume for the interconnects. The restrictions of size and area mayimpact the electrical resistance and reliability of theinterconnections.

In other respects, a battery may contain a liquid electrolyte whichcould boil at high temperature. This restriction may directly competewith the desire to use a solder interconnect which may, for example,require relatively high temperatures such as 250 degrees Celsius tomelt. Although in some examples, the battery chemistry, including theelectrolyte, and the heat source used to form solder basedinterconnects, may be isolated spatially from each other. In the casesof emerging biomedical devices, the small size may preclude theseparation of electrolyte and solder joints by sufficient distance toreduce heat conduction.

Interconnects

Interconnects may allow current to flow to and from the battery inconnection with an external circuit. Such interconnects may interfacewith the environments inside and outside the battery, and may cross theboundary or seal between those environments. These interconnects may beconsidered as traces, making connections to an external circuit, passingthrough the battery seal, and then connecting to the current collectorsinside the battery. As such, these interconnects may have severalrequirements. Outside the battery, the interconnects may resembletypical printed circuit traces. They may be soldered to, or otherwiseconnect to, other traces. In an example where the battery is a separatephysical element from a circuit board comprising an integrated circuit,the battery interconnect may allow for connection to the externalcircuit. This connection may be formed with solder, conductive tape,conductive ink or epoxy, or other means. The interconnect traces mayneed to survive in the environment outside the battery, for example, notcorroding in the presence of oxygen.

As the interconnect passes through the battery seal, it may be ofcritical importance that the interconnect coexist with the seal andpermit sealing. Adhesion may be required between the seal andinterconnect in addition to the adhesion which may be required betweenthe seal and battery package. Seal integrity may need to be maintainedin the presence of electrolyte and other materials inside the battery.Interconnects, which may typically be metallic, may be known as pointsof failure in battery packaging. The electrical potential and/or flow ofcurrent may increase the tendency for electrolyte to “creep” along theinterconnect. Accordingly, an interconnect may need to be engineered tomaintain seal integrity.

Inside the battery, the interconnects may interface with the currentcollectors or may actually form the current collectors. In this regard,the interconnect may need to meet the requirements of the currentcollectors as described herein, or may need to form an electricalconnection to such current collectors.

One class of candidate interconnects and current collectors is metalfoils. Such foils are available in thickness of 25 microns or less,which make them suitable for very thin batteries. Such foil may also besourced with low surface roughness and contamination, two factors whichmay be critical for battery performance. The foils may include zinc,nickel, brass, copper, titanium, other metals, and various alloys.

Electrolyte

An electrolyte is a component of a battery which facilitates a chemicalreaction to take place between the chemical materials of the electrodes.Typical electrolytes may be electrochemically active to the electrodes,for example, allowing oxidation and reduction reactions to occur. Insome examples, this important electrochemical activity may make for achallenge to creating devices that are biocompatible. For example,potassium hydroxide (KOH) may be a commonly used electrolyte in alkalinecells. At high concentration the material has a high pH and may interactunfavorably with various living tissues. On the other hand, in someexamples, electrolytes may be employed which may be lesselectrochemically active; however, these materials may typically resultin reduced electrical performance, such as reduced cell voltage andincreased cell resistance. Accordingly, one key aspect of the design andengineering of a biomedical microbattery may be the electrolyte. It maybe desirable for the electrolyte to be sufficiently active to meetelectrical requirements while also being relatively safe for use in- oron-body.

Various test scenarios may be used to determine the safety of batterycomponents, in particular electrolytes, to living cells. These results,in conjunction with tests of the battery packaging, may allowengineering design of a battery system that may meet requirements. Forexample, when developing a powered contact lens, battery electrolytesmay be tested on a human corneal cell model. These tests may includeexperiments on electrolyte concentration, exposure time, and additives.The results of such tests may indicate cell metabolism and otherphysiological aspects. Tests may also include in-vivo testing on animalsand humans.

Electrolytes for use in the present invention may include zinc chloride,zinc acetate, ammonium acetate, and ammonium chloride in massconcentrations from approximately 0.1 percent to 50 percent, and in anon-limiting example may be approximately 25 percent. The specificconcentrations may depend on electrochemical activity, batteryperformance, shelf life, seal integrity, and biocompatibility.

In some examples, several classes of additives may be utilized in thecomposition of a battery system. Additives may be mixed into theelectrolyte base to alter its characteristics. For example, gellingagents such as agar may reduce the ability of the electrolyte to leakout of packing, thereby increasing safety. Corrosion inhibitors may beadded to the electrolyte, for example, to improve shelf life by reducingthe undesired dissolution of the zinc anode into the electrolyte. Theseinhibitors may positively or adversely affect the safety profile of thebattery. Wetting agents or surfactants may be added, for example, toallow the electrolyte to wet the separator or to be filled into thebattery package. Again, these wetting agents may be positive or negativefor safety. The addition of surfactant to the electrolyte may increasethe electrical impedance of the cell. Accordingly, the lowestconcentration of surfactant to achieve the desired wetting or otherproperties should be used. Exemplary surfactants may include Triton™X-100, Triton™ QS44, and Dowfax™ 3B2 in concentrations from 0.01 percentto 2 percent.

Novel electrolytes are also emerging which may dramatically improve thesafety profile of biomedical microbatteries. For example, a class ofsolid electrolytes may be inherently resistant to leaking while stilloffering suitable electrical performance.

Batteries using “salt water” electrolyte are commonly used in reservecells for marine use. Torpedoes, buoys, and emergency lights may usesuch batteries. Reserve cells are batteries in which the activematerials, the electrodes and electrolyte, are separated until the timeof use. Because of this separation, the cells' self-discharge is greatlyreduced and shelf life is greatly increased. Salt water batteries may bedesigned from a variety of electrode materials, including zinc,magnesium, aluminum, copper, tin, manganese dioxide, and silver oxide.The electrolyte may be actual sea water, for example, water from theocean flooding the battery upon contact, or may be a speciallyengineered saline formulation. This type of battery may be particularlyuseful in contact lenses. A saline electrolyte may have superiorbiocompatibility to classical electrolytes such as potassium hydroxideand zinc chloride. Contact lenses are stored in a “packing solution”which is typically a mixture of sodium chloride, perhaps with othersalts and buffering agents. This solution has been demonstrated as abattery electrolyte in combination with a zinc anode and manganesedioxide cathode. Other electrolyte and electrode combinations arepossible. A contact lens using a “salt water” battery may comprise anelectrolyte based on sodium chloride, packing solution, or even aspecially engineered electrolyte similar to tear fluid. Such a batterycould, for example, be activated with packing solution, maintain anopening to the eye, and continue operating with exposure to human tears.

In addition to, or instead of, possible benefits for biocompatibility byusing an electrolyte more similar to tears, or actually using tears, areserve cell may be used to meet the shelf life requirements of acontact lens product. Typical contact lenses are specified for storageof 3 years or more. This is a challenging requirement for a battery witha small and thin package. A reserve cell for use in a contact lens mayhave a design similar to those shown in FIGS. 1 and 3, but theelectrolyte might not be added at the time of manufacture. Theelectrolyte may be stored in an ampule within the contact lens andconnected to the battery, or saline surrounding the battery may be usedas the electrolyte. Within the contact lens and battery package, a valveor port may be designed to separate the electrolyte from the electrodesuntil the user activates the lens. Upon activation, perhaps by simplypinching the edge of the contact lens (similar to activating a glowstick), the electrolyte may be allowed to flow into the battery and forman ionic pathway between the electrodes. This may involve a one-timetransfer of electrolyte or may expose the battery for continueddiffusion.

Some battery systems may use or consume electrolyte during the chemicalreaction. Accordingly, it may be necessary to engineer a certain volumeof electrolyte into the packaged system. This electrolyte may be storedin various locations including the separator or a reservoir.

In some examples, a design of a battery system may include a componentor components that may function to limit discharge capacity of thebattery system. For example, it may be desirable to design the materialsand amounts of materials of the anode, cathode, or electrolyte such thatone of them may be depleted first during the course of reactions in thebattery system. In such an example, the depletion of one of the anode,cathode, or electrolyte may reduce the potential for problematicdischarge and side reactions to not take place at lower dischargevoltages. These problematic reactions may produce, for example,excessive gas or byproducts which could be detrimental to safety andother factors.

Modular Battery Components

In some examples, a modular battery component may be formed according tosome aspects and examples of the present invention. In these examples,the modular battery assembly may be a separate component from otherparts of the biomedical device. In the example of an ophthalmic contactlens device, such a design may include a modular battery that isseparate from the rest of a media insert. There may be numerousadvantages of forming a modular battery component. For example, in theexample of the contact lens, a modular battery component may be formedin a separate, non-integrated process which may alleviate the need tohandle rigid, three-dimensionally formed optical plastic components. Inaddition, the sources of manufacturing may be more flexible and mayoperate in a more parallel mode to the manufacturing of the othercomponents in the biomedical device. Furthermore, the fabrication of themodular battery components may be decoupled from the characteristics ofthree-dimensional (3D) shaped devices. For example, in applicationsrequiring three-dimensional final forms, a modular battery system may befabricated in a flat or roughly two-dimensional (2D) perspective andthen shaped to the appropriate three-dimensional shape. A modularbattery component may be tested independently of the rest of thebiomedical device and yield loss due to battery components may be sortedbefore assembly. The resulting modular battery component may be utilizedin various media insert constructs that do not have an appropriate rigidregion upon which the battery components may be formed; and, in a stillfurther example, the use of modular battery components may facilitatethe use of different options for fabrication technologies than mightotherwise be utilized, such as, web-based technology (roll to roll),sheet-based technology (sheet-to-sheet), printing, lithography, and“squeegee” processing. In some examples of a modular battery, thediscrete containment aspect of such a device may result in additionalmaterial being added to the overall biomedical device construct. Sucheffects may set a constraint for the use of modular battery solutionswhen the available space parameters require minimized thickness orvolume of solutions.

Battery shape requirements may be driven at least in part by theapplication for which the battery is to be used. Traditional batteryform factors may be cylindrical forms or rectangular prisms, made ofmetal, and may be geared toward products which require large amounts ofpower for long durations. These applications may be large enough thatthey may comprise large form factor batteries. In another example,planar (2D) solid-state batteries are thin rectangular prisms, typicallyformed upon inflexible silicon or glass. These planar solid-statebatteries may be formed in some examples using silicon wafer-processingtechnologies. In another type of battery form factor, low power,flexible batteries may be formed in a pouch construct, using thin foilsor plastic to contain the battery chemistry. These batteries may be madeflat (2D), and may be designed to function when bowed to a modestout-of-plane (3D) curvature.

In some of the examples of the battery applications in the presentinvention where the battery may be employed in a variable optic lens,the form factor may require a three-dimensional curvature of the batterycomponent where a radius of that curvature may be on the order ofapproximately 8.4 mm. The nature of such a curvature may be consideredto be relatively steep and for reference may approximate the type ofcurvature found on a human fingertip. The nature of a relative steepcurvature creates challenging aspects for manufacture. In some examplesof the present invention, a modular battery component may be designedsuch that it may be fabricated in a flat, two-dimensional manner andthen formed into a three-dimensional form of relative high curvature.

Battery Module Thickness

In designing battery components for biomedical applications, tradeoffsamongst the various parameters may be made balancing technical, safetyand functional requirements. The thickness of the battery component maybe an important and limiting parameter. For example, in an optical lensapplication the ability of a device to be comfortably worn by a user mayhave a critical dependence on the thickness across the biomedicaldevice. Therefore, there may be critical enabling aspects in designingthe battery for thinner results. In some examples, battery thickness maybe determined by the combined thicknesses of top and bottom sheets,spacer sheets, and adhesive layer thicknesses. Practical manufacturingaspects may drive certain parameters of film thickness to standardvalues in available sheet stock. In addition, the films may have minimumthickness values to which they may be specified base upon technicalconsiderations relating to chemical compatibility, moisture/gasimpermeability, surface finish, and compatibility with coatings that maybe deposited upon the film layers.

In some examples, a desired or goal thickness of a finished batterycomponent may be a component thickness that is less than 220 μm. Inthese examples, this desired thickness may be driven by thethree-dimensional geometry of an exemplary ophthalmic lens device wherethe battery component may need to be fit inside the available volumedefined by a hydrogel lens shape given end user comfort,biocompatibility, and acceptance constraints. This volume and its effecton the needs of battery component thickness may be a function of totaldevice thickness specification as well as device specification relatingto its width, cone angle, and inner diameter. Another important designconsideration for the resulting battery component design may relate tothe volume available for active battery chemicals and materials in agiven battery component design with respect to the resulting chemicalenergy that may result from that design. This resulting chemical energymay then be balanced for the electrical requirements of a functionalbiomedical device for its targeted life and operating conditions

Battery Module Flexibility

Another dimension of relevance to battery design and to the design ofrelated devices that utilize battery based energy sources is theflexibility of the battery component. There may be numerous advantagesconferred by flexible battery forms. For example, a flexible batterymodule may facilitate the previously mentioned ability to fabricate thebattery form in a two-dimensional (2D) flat form. The flexibility of theform may allow the two-dimensional battery to then be formed into anappropriate 3D shape to fit into a biomedical device such as a contactlens.

In another example of the benefits that may be conferred by flexibilityin the battery module, if the battery and the subsequent device isflexible then there may be advantages relating to the use of the device.In an example, a contact lens form of a biomedical device may haveadvantages for insertion/removal of the media insert based contact lensthat may be closer to the insertion/removal of a standard, non-filledhydrogel contact lens.

The number of flexures may be important to the engineering of thebattery. For example, a battery which may only flex one time from aplanar form into a shape suitable for a contact lens may havesignificantly different design from a battery capable of multipleflexures. The flexure of the battery may also extend beyond the abilityto mechanically survive the flexure event. For example, an electrode maybe physically capable of flexing without breaking, but the mechanicaland electrochemical properties of the electrode may be altered byflexure. Flex-induced changes may appear instantly, for example, aschanges to impedance, or flexure may introduce changes which are onlyapparent in long-term shelf life testing.

Battery Module Width

There may be numerous applications into which the biocompatibleenergization elements or batteries of the present invention may beutilized. In general, the battery width requirement may be largely afunction of the application in which it is applied. In an exemplarycase, a contact lens battery system may have constrained needs for thespecification on the width of a modular battery component. In someexamples of an ophthalmic device where the device has a variable opticfunction powered by a battery component, the variable optic portion ofthe device may occupy a central spherical region of about 7.0 mm indiameter. The exemplary battery elements may be considered as athree-dimensional object, which fits as an annular, conical skirt aroundthe central optic and formed into a truncated conical ring. If therequired maximum diameter of the rigid insert is a diameter of 8.50 mm,and tangency to a certain diameter sphere may be targeted (as forexample in a roughly 8.40 mm diameter), then geometry may dictate whatthe allowable battery width may be. There may be geometric models thatmay be useful for calculating desirable specifications for the resultinggeometry which in some examples may be termed a conical frustumflattened into a sector of an annulus.

Flattened battery width may be driven by two features of the batteryelement, the active battery components and seal width. In some examplesrelating to ophthalmic devices a target thickness may be between 0.100mm and 0.500 mm per side, and the active battery components may betargeted at roughly 0.800 mm wide. Other biomedical devices may havediffering design constraints but the principles for flexible flatbattery elements may apply in similar fashion.

Cavities as Design Elements in Battery Component Design

In some examples, battery elements may be designed in manners thatsegment the regions of active battery chemistry. There may be numerousadvantages from the division of the active battery components intodiscrete segments. In a non-limiting example, the fabrication ofdiscrete and smaller elements may facilitate production of the elements.The function of battery elements including numerous smaller elements maybe improved. Defects of various kinds may be segmented andnon-functional elements may be isolated in some cases to result indecreased loss of function. This may be relevant in examples where theloss of battery electrolyte may occur. The isolation of individualizedcomponents may allow for a defect that results in leakage of electrolyteout of the critical regions of the battery to limit the loss of functionto that small segment of the total battery element whereas theelectrolyte loss through the defect could empty a significantly largerregion for batteries configured as a single cell. Smaller cells mayresult in lowered volume of active battery chemicals on an overallperspective, but the mesh of material surrounding each of the smallercells may result in a strengthening of the overall structure.

Battery Element Internal Seals

In some examples of battery elements for use in biomedical devices, thechemical action of the battery involves aqueous chemistry, where wateror moisture is an important constituent to control. Therefore it may beimportant to incorporate sealing mechanisms that retard or prevent themovement of moisture either out of or into the battery body. Moisturebarriers may be designed to keep the internal moisture level at adesigned level, within some tolerance. In some examples, a moisturebarrier may be divided into two sections or components; namely, thepackage and the seal.

The package may refer to the main material of the enclosure. In someexamples, the package may comprise a bulk material. The Water VaporTransmission Rate (WVTR) may be an indicator of performance, with ISO,ASTM standards controlling the test procedure, including theenvironmental conditions operant during the testing. Ideally, the WVTRfor a good battery package may be “zero.” Exemplary materials with anear-zero WVTR may be glass and metal foils. Plastics, on the otherhand, may be inherently porous to moisture, and may vary significantlyfor different types of plastic. Engineered materials, laminates, orco-extrudes may usually be hybrids of the common package materials.

The seal may be the interface between two of the package surfaces. Theconnecting of seal surfaces finishes the enclosure along with thepackage. In many examples, the nature of seal designs may make themdifficult to characterize for the seal's WVTR due to difficulty inperforming measurements using an ISO or ASTM standard, as the samplesize or surface area may not be compatible with those procedures. Insome examples, a practical manner to testing seal integrity may be afunctional test of the actual seal design, for some defined conditions.Seal performance may be a function of the seal material, the sealthickness, the seal length, the seal width, and the seal adhesion orintimacy to package substrates.

In some examples, seals may be formed by a welding process that mayinvolve thermal, laser, solvent, friction, ultrasonic, or arcprocessing. In other examples, seals may be formed through the use ofadhesive sealants such as glues, epoxies, acrylics, natural rubber, andsynthetic rubber. Other examples may derive from the utilization ofgasket type material that may be formed from cork, natural and syntheticrubber, polytetrafluoroethylene (PTFE), polypropylene, and silicones tomention a few non-limiting examples.

In some examples, the batteries according to the present invention maybe designed to have a specified operating life. The operating life maybe estimated by determining a practical amount of moisture permeabilitythat may be obtained using a particular battery system and thenestimating when such a moisture leakage may result in an end of lifecondition for the battery. For example, if a battery is stored in a wetenvironment, then the partial pressure difference between inside andoutside the battery will be minimal, resulting in a reduced moistureloss rate, and therefore the battery life may be extended. The sameexemplary battery stored in a particularly dry and hot environment mayhave a significantly reduced expectable lifetime due to the strongdriving function for moisture loss.

Battery Element Separators

Batteries of the type described in the present invention may utilize aseparator material that physically and electrically separates the anodeand anode current collector portions from the cathode and cathodecurrent collector portions. The separator may be a membrane that ispermeable to water and dissolved electrolyte components; however, it maytypically be electrically non-conductive. While a myriad ofcommercially-available separator materials may be known to those ofskill in the art, the novel form factor of the present invention maypresent unique constraints on the task of separator selection,processing, and handling.

Since the designs of the present invention may have ultra-thin profiles,the choice may be limited to the thinnest separator materials typicallyavailable. For example, separators of approximately 25 microns inthickness may be desirable. Some examples which may be advantageous maybe about 12 microns in thickness. There may be numerous acceptablecommercial separators include microfibrillated, microporous polyethylenemonolayer and/or polypropylene-polyethylene-polypropylene (PP/PE/PP)trilayer separator membranes such as those produced by Celgard(Charlotte, N.C.). A desirable example of separator material may beCelgard M824 PP/PE/PP trilayer membrane having a thickness of 12microns. Alternative examples of separator materials useful for examplesof the present invention may include separator membranes includingregenerated cellulose (e.g. cellophane).

While PP/PE/PP trilayer separator membranes may have advantageousthickness and mechanical properties, owing to their polyolefiniccharacter, they may also suffer from a number of disadvantages that mayneed to be overcome in order to make them useful in examples of thepresent invention. Roll or sheet stock of PP/PE/PP trilayer separatormaterials may have numerous wrinkles or other form errors that may bedeleterious to the micron-level tolerances applicable to the batteriesdescribed herein. Furthermore, polyolefin separators may need to be cutto ultra-precise tolerances for inclusion in the present designs, whichmay therefore implicate laser cutting as an exemplary method of formingdiscrete current collectors in desirable shapes with tight tolerances.Owing to the polyolefinic character of these separators, certain cuttinglasers useful for micro fabrication may employ laser wavelengths, e.g.355 nm, that will not cut polyolefins. The polyolefins do notappreciably absorb the laser energy and are thereby non-ablatable.Finally, polyolefin separators may not be inherently wettable to aqueouselectrolytes used in the batteries described herein.

Nevertheless, there may be methods for overcoming these inherentlimitations for polyolefinic type membranes. In order to present amicroporous separator membrane to a high-precision cutting laser forcutting pieces into arc segments or other advantageous separatordesigns, the membrane may need to be flat and wrinkle-free. If these twoconditions are not met, the separator membrane may not be fully cutbecause the cutting beam may be inhibited as a result of defocusing ofor otherwise scattering the incident laser energy. Additionally, if theseparator membrane is not flat and wrinkle-free, the form accuracy andgeometric tolerances of the separator membrane may not be sufficientlyachieved. Allowable tolerances for separators of current examples maybe, for example, +0 microns and −20 microns with respect tocharacteristic lengths and/or radii. There may be advantages for tightertolerances of +0 microns and −10 micron and further for tolerances of +0microns and −5 microns. Separator stock material may be made flat andwrinkle-free by temporarily laminating the material to a float glasscarrier with an appropriate low-volatility liquid. Low-volatilityliquids may have advantages over temporary adhesives due to thefragility of the separator membrane and due to the amount of processingtime that may be required to release separator membrane from an adhesivelayer. Furthermore, in some examples achieving a flat and wrinkle-freeseparator membrane on float glass using a liquid has been observed to bemuch more facile than using an adhesive. Prior to lamination, theseparator membrane may be made free of particulates. This may beachieved by ultrasonic cleaning of separator membrane to dislodge anysurface-adherent particulates. In some examples, handling of a separatormembrane may be done in a suitable, low-particle environment such as alaminar flow hood or a cleanroom of at least class 10,000. Furthermore,the float glass substrate may be made to be particulate free by rinsingwith an appropriate solvent, ultrasonic cleaning, and/or wiping withclean room wipes.

While a wide variety of low-volatility liquids may be used for themechanical purpose of laminating microporous polyolefin separatormembranes to a float glass carrier, specific requirements may be imposedon the liquid to facilitate subsequent laser cutting of discreteseparator shapes. One requirement may be that the liquid has a surfacetension low enough to soak into the pores of the separator materialwhich may easily be verified by visual inspection. In some examples, theseparator material turns from a white color to a translucent appearancewhen liquid fills the micropores of the material. It may be desirable tochoose a liquid that may be benign and “safe” for workers that will beexposed to the preparation and cutting operations of the separator. Itmay be desirable to choose a liquid whose vapor pressure may be lowenough so that appreciable evaporation does not occur during the timescale of processing (on the order of 1 day). Finally, in some examplesthe liquid may have sufficient solvating power to dissolve advantageousUV absorbers that may facilitate the laser cutting operation. In anexample, it has been observed that a 12 percent (w/w) solution ofavobenzone UV absorber in benzyl benzoate solvent may meet theaforementioned requirements and may lend itself to facilitating thelaser cutting of polyolefin separators with high precision and tolerancein short order without an excessive number of passes of the cuttinglaser beam. In some examples, separators may be cut with an 8 W 355 nmnanosecond diode-pumped solid state laser using this approach where thelaser may have settings for low power attenuation (e.g. 3 percentpower), a moderate speed of 1 to 10 mm/s, and only 1 to 3 passes of thelaser beam. While this UV-absorbing oily composition has been proven tobe an effective laminating and cutting process aid, other oilyformulations may be envisaged by those of skill in the art and usedwithout limitation.

In some examples, a separator may be cut while fixed to a float glass.One advantage of laser cutting separators while fixed to a float glasscarrier may be that a very high number density of separators may be cutfrom one separator stock sheet much like semiconductor die may bedensely arrayed on a silicon wafer. Such an approach may provide economyof scale and parallel processing advantages inherent in semiconductorprocesses. Furthermore, the generation of scrap separator membrane maybe minimized. Once separators have been cut, the oily process aid fluidmay be removed by a series of extraction steps with miscible solvents,the last extraction may be performed with a high-volatility solvent suchas isopropyl alcohol in some examples. Discrete separators, onceextracted, may be stored indefinitely in any suitable low-particleenvironment.

As previously mentioned polyolefin separator membranes may be inherentlyhydrophobic and may need to be made wettable to aqueous surfactants usedin the batteries of the present invention. One approach to make theseparator membranes wettable may be oxygen plasma treatment. Forexample, separators may be treated for 1 to 5 minutes in a 100 percentoxygen plasma at a wide variety of power settings and oxygen flow rates.While this approach may improve wettability for a time, it may bewell-known that plasma surface modifications provide a transient effectthat may not last long enough for robust wetting of electrolytesolutions. Another approach to improve wettability of separatormembranes may be to treat the surface by incorporating a suitablesurfactant on the membrane. In some cases, the surfactant may be used inconjunction with a hydrophilic polymeric coating that remains within thepores of the separator membrane.

Another approach to provide more permanence to the hydrophilicityimparted by an oxidative plasma treatment may be by subsequent treatmentwith a suitable hydrophilic organosilane. In this manner, the oxygenplasma may be used to activate and impart functional groups across theentire surface area of the microporous separator. The organosilane maythen covalently bond to and/or non-covalently adhere to the plasmatreated surface. In examples using an organosilane, the inherentporosity of the microporous separator may not be appreciably changed,monolayer surface coverage may also be possible and desired. Prior artmethods incorporating surfactants in conjunction with polymeric coatingsmay require stringent controls over the actual amount of coating appliedto the membrane, and may then be subject to process variability. Inextreme cases, pores of the separator may become blocked, therebyadversely affecting utility of the separator during the operation of theelectrochemical cell. An exemplary organosilane useful in the presentinvention may be (3-aminopropyl)triethoxysilane. Other hydrophilicorganosilanes may be known to those of skill in the art and may be usedwithout limitation.

Still another method for making separator membranes wettable by aqueouselectrolyte may be the incorporation of a suitable surfactant in theelectrolyte formulation. One consideration in the choice of surfactantfor making separator membranes wettable may be the effect that thesurfactant may have on the activity of one or more electrodes within theelectrochemical cell, for example, by increasing the electricalimpedance of the cell. In some cases, surfactants may have advantageousanti-corrosion properties, specifically in the case of zinc anodes inaqueous electrolytes. Zinc may be an example known to undergo a slowreaction with water to liberate hydrogen gas, which may be undesirable.Numerous surfactants may be known by those of skill in the art to limitrates of said reaction to advantageous levels. In other cases, thesurfactant may so strongly interact with the zinc electrode surface thatbattery performance may be impeded. Consequently, much care may need tobe made in the selection of appropriate surfactant types and loadinglevels to ensure that separator wettability may be obtained withoutdeleteriously affecting electrochemical performance of the cell. In somecases, a plurality of surfactants may be used, one being present toimpart wettability to the separator membrane and the other being presentto facilitate anti-corrosion properties to the zinc anode. In oneexample, no hydrophilic treatment is done to the separator membrane anda surfactant or plurality of surfactants is added to the electrolyteformulation in an amount sufficient to effect wettability of theseparator membrane.

Discrete separators may be integrated into the laminar microbattery bydirect placement into a means for storage including a designed cavity,pocket, or structure within the assembly. Desirably, this storage meansmay be formed by a laminar structure having a cutout, which may be ageometric offset of the separator shape, resulting in a cavity, pocket,or structure within the assembly. Furthermore, the storage means mayhave a ledge or step on which the separator rests during assembly. Theledge or step may optionally include a pressure-sensitive adhesive whichretains the discrete separator. Advantageously, the pressure-sensitiveadhesive may be the same one used in the construction and stack up ofother elements of an exemplary laminar microbattery.

Pressure Sensitive Adhesive

In some examples, the plurality of components comprising the laminarmicrobatteries of the present invention may be held together with apressure-sensitive adhesive (PSA) that also serves as a sealant. While amyriad of commercially available pressure-sensitive adhesiveformulations may exist, such formulations almost always includecomponents that may make them unsuitable for use within a biocompatiblelaminar microbattery. Examples of undesirable components inpressure-sensitive adhesives may include low molecular mass leachablecomponents, antioxidants e.g. BHT and/or MEHQ, plasticizing oils,impurities, oxidatively unstable moieties containing, for example,unsaturated chemical bonds, residual solvents and/or monomers,polymerization initiator fragments, polar tackifiers, and the like.

Suitable PSAs may on the other hand exhibit the following properties.They may be able to be applied to laminar components to achieve thinlayers on the order of 2 to 20 microns. As well, they may comprise aminimum of, for example, zero undesirable or non-biocompatiblecomponents. Additionally, they may have sufficient adhesive and cohesiveproperties so as to bind the components of the laminar battery together.And, they may be able to flow into the micron-scale features inherent indevices of the present construction while providing for a robust sealingof electrolyte within the battery. In some examples of suitable PSAs,the PSAs may have a low permeability to water vapor in order to maintaina desirable aqueous electrolyte composition within the battery even whenthe battery may be subjected to extremes in humidity for extendedperiods of time. The PSAs may have good chemical resistance tocomponents of electrolytes such as acids, surfactants, and salts. Theymay be inert to the effects of water immersion. Suitable PSAs may have alow permeability to oxygen to minimize the rate of direct oxidation,which may be a form of self-discharge, of zinc anodes. And, they mayfacilitate a finite permeability to hydrogen gas, which may be slowlyevolved from zinc anodes in aqueous electrolytes. This property offinite permeability to hydrogen gas may avoid a build-up of internalpressure.

In consideration of these requirements, polyisobutylene (PIB) may be acommercially-available material that may be formulated into PSAcompositions meeting many if not all desirable requirements.Furthermore, PIB may be an excellent barrier sealant with very low waterabsorbance and low oxygen permeability. An example of PIB useful in theexamples of the present invention may be Oppanol® B15 by BASFCorporation. Oppanol® B15 may be dissolved in hydrocarbon solvents suchas toluene, heptane, dodecane, mineral spirits, and the like. Oneexemplary PSA composition may include 30 percent Oppanol® B15 (w/w) in asolvent mixture including 70 percent (w/w) toluene and 30 percentdodecane. The adhesive and rheological properties of PIB based PSA's maybe determined in some examples by the blending of different molecularmass grades of PIB. A common approach may be to use a majority of lowmolar mass PIB, e.g. Oppanol® B10 to affect wetting, tack, and adhesion,and to use a minority of high molar mass PIB to effect toughness andresistance to flow. Consequently, blends of any number of PIB molar massgrades may be envisioned and may be practiced within the scope of thepresent invention. Furthermore, tackifiers may be added to the PSAformulation so long as the aforementioned requirements may be met. Bytheir very nature, tackifiers impart polar properties to PSAformulations, so they may need to be used with caution so as to notadversely affect the barrier properties of the PSA. Furthermore,tackifiers may in some cases be oxidatively unstable and may include anantioxidant, which could leach out of the PSA. For these reasons,exemplary tackifiers for use in PSA's for biocompatible laminarmicrobatteries may include fully- or mostly hydrogenated hydrocarbonresin tackifiers such as the Regalrez series of tackifiers from EastmanChemical Corporation.

Additional Package and Substrate Considerations in Biocompatible BatteryModules

There may be numerous packaging and substrate considerations that maydictate desirable characteristics for package designs used inbiocompatible laminar microbatteries. For example, the packaging maydesirably be predominantly foil and/or film based where these packaginglayers may be as thin as possible, for example, 10 to 50 microns.Additionally, the packaging may provide a sufficient diffusion barrierto moisture gain or loss during the shelf life. In many desirableexamples, the packaging may provide a sufficient diffusion barrier tooxygen ingress to limit degradation of zinc anodes by direct oxidation.

In some examples, the packaging may provide a finite permeation pathwayto hydrogen gas that may evolve due to direct reduction of water byzinc. And, the packaging may desirably sufficiently contain and mayisolate the contents of the battery such that potential exposure to auser may be minimized.

In the present invention, packaging constructs may include the followingtypes of functional components: top and bottom packaging layers, PSAlayers, spacer layers, interconnect zones, filling ports, and secondarypackaging.

In some examples, top and bottom packaging layers may comprise metallicfoils or polymer films. Top and bottom packaging layers may comprisemulti-layer film constructs containing a plurality of polymer and/orbarrier layers. Such film constructs may be referred to as coextrudedbarrier laminate films. An example of a commercial coextruded barrierlaminate film of particular utility in the present invention may be 3M®Scotchpak 1109 backing which consists of a polyethylene terephthalate(PET) carrier web, a vapor-deposited aluminum barrier layer, and apolyethylene layer including a total average film thickness of 33microns. Numerous other similar multilayer barrier films may beavailable and may be used in alternate examples of the presentinvention.

In design constructions including a PSA, packaging layer surfaceroughness may be of particular importance because the PSA may also needto seal opposing packaging layer faces. Surface roughness may resultfrom manufacturing processes used in foil and film production, forexample, processes employing rolling, extruding, embossing and/orcalendaring, among others. If the surface is too rough, PSA may be notable to be applied in a uniform thickness when the desired PSA thicknessmay be on the order of the surface roughness Ra (the arithmetic averageof the roughness profile). Furthermore, PSA's may not adequately sealagainst an opposing face if the opposing face has roughness that may beon the order of the PSA layer thickness. In the present invention,packaging materials having a surface roughness, Ra, less than 10 micronsmay be acceptable examples. In some examples, surface roughness valuesmay be 5 microns or less. And, in still further examples, the surfaceroughness may be 1 micron or less. Surface roughness values may bemeasured by a variety of methods including but not limited tomeasurement techniques such as white light interferometry, stylusprofilometry, and the like. There may be many examples in the art ofsurface metrology that surface roughness may be described by a number ofalternative parameters and that the average surface roughness, Ra,values discussed herein may be meant to be representative of the typesof features inherent in the aforementioned manufacturing processes.

Exemplary Illustrated Processing of Biocompatible Energization—PlacedSeparator

An example of the steps that may be involved in processing biocompatibleenergization elements may be found referring to FIGS. 4A-4N. Theprocessing at some of the exemplary steps may be found in the individualfigures. In FIG. 4A, a combination of a PET Cathode Spacer 401 and a PETGap Spacer 404 may be illustrated. The PET Cathode Spacer 401 may beformed by applying films of PET 403 which, for example, may be roughly 3mils thick. On either side of the PET layer may be found PSA layers orthese may be capped with a PVDF release layer 402 which may be roughly 1mil in thickness. The PET Gap spacer 404 may be formed of a PVDF layer409 which may be roughly 3 mils in thickness. There may be a capping PETlayer 405 which may be roughly 0.5 mils in thickness. Between the PVDFlayer 409 and the capping PET layer 405, in some examples, may be alayer of PSA.

Proceeding to FIG. 4B, a hole 406 in the PET Gap spacer layer 404 may becut by laser cutting treatment. Next at FIG. 4C, the cut PET Gap spacerlayer 404 may be laminated 408 to the PET Cathode Spacer layer 401.Proceeding to FIG. 4D, a cathode spacer hole 410 may be cut by lasercutting treatment. The alignment of this cutting step may be registeredto the previously cut features in the PET Gap spacer layer 404. At FIG.4E, a layer of Celgard 412, for an ultimate separator layer, may bebonded to a carrier 411. Proceeding to FIG. 4F, the Celgard material maybe cut to figures that are between the size of the previous two lasercut holes, and approximately the size of the hole 406 in the PET Gapspacer 404, forming a precut separator 420. Proceeding to FIG. 4G, apick and place tool 421 may be used to pick and place discrete pieces ofCelgard into their desired locations on the growing device. At FIG. 4H,the placed Celgard pieces 422 are fastened into place and then the PVDFrelease layer 423 may be removed. Proceeding to FIG. 4I, the growingdevice structure may be bonded to a film of the anode 425. The anode 425may comprise an anode collector film upon which a zinc anode film hasbeen electrodeposited.

Proceeding to FIG. 4J, a cathode slurry 430 may be placed into theformed gap. A squeegee 431 may be used in some examples to spread thecathode mix across a work piece and in the process fill the gaps of thebattery devices being formed. After filling, the remaining PVDF releaselayer 432 may be removed which may result in the structure illustratedin FIG. 4K. At FIG. 4L the entire structure may be subjected to a dryingprocess which may shrink the cathode slurry 440 to also be at the heightof the PET layer top. Proceeding to FIG. 4M, a cathode film layer 450,which may already have the cathode collector film upon it, may be bondedto the growing structure. At FIG. 4N a laser cutting process may beperformed to remove side regions 460 and yield a battery element 470.There may be numerous alterations, deletions, changes to materials andthickness targets that may be useful within the intent of the presentinvention.

The result of the exemplary processing may be depicted in some detail atFIG. 5. In an example, the following reference features may be defined.The cathode chemistry 510 may be located in contact with the cathode andcathode collector 520. A pressure-sensitive adhesive layer 530 may holdand seal the cathode collector 520 to a PET Spacer layer 540. On theother side of the PET Spacer layer 540 may be another PSA layer 550,which seals and adheres the PET Spacer layer 540 to the PET Gap layer560. Another PSA layer 565 may seal and adhere the PET Gap layer 560 tothe Anode and Anode Current Collector layers. A zinc plated layer 570may be plated onto the Anode Current Collector 580. The separator layer590 may be located within the structure to perform the associatedfunctions as have been defined in the present invention. In someexamples, an electrolyte may be added during the processing of thedevice, in other examples, the separator may already includeelectrolyte.

Exemplary Processing Illustration of BiocompatibleEnergization—Deposited Separator

An example of the steps that may be involved in processing biocompatibleenergization elements may be found in FIGS. 6A-6F. The processing atsome of the exemplary steps may be found in the individual figures.There may be numerous alterations, deletions, changes to materials andthickness targets that may be useful within the intent of the presentinvention.

In FIG. 6A, an exemplary laminar construct 600 is illustrated. Thelaminar structure may comprise two laminar construct release layers, 602and 602 a; two laminar construct adhesive layers 604 and 604 a, locatedbetween the laminar construct release layers 602 and 602 a; and alaminar construct core 606, located between the two laminar constructadhesive layers 604 and 604 a. The laminar construct release layers, 602and 602 a, and adhesive layers, 604 and 604 a, may be produced orpurchased, such as a commercially available pressure-sensitive adhesivetransfer tape with primary liner layer. The laminar construct adhesivelayers may be a PVDF layer which may be approximately 1-3 millimeters inthickness and cap the laminar construct core 606. The laminar constructcore 606 may comprise a thermoplastic polymer resin such as polyethyleneterephthalate, which, for example, may be roughly 3 millimeters thick.Proceeding to FIG. 6B, a means for storing the cathode mixture, such asa cavity for the cathode pocket 608, may be cut in the laminar constructby laser cutting treatment.

Next, at FIG. 6C, the bottom laminar construct release layer 602 a maybe removed from the laminar construct, exposing the laminar constructadhesive layer 604 a. The laminar construct adhesive layer 604 a maythen be used to adhere an anode connection foil 610 to cover the bottomopening of the cathode pocket 608. Proceeding to FIG. 6D, the anodeconnection foil 610 may be protected on the exposed bottom layer byadhering a masking layer 612. The masking layer 612 may be acommercially available PSA transfer tape with a primary liner. Next, atFIG. 6E, the anode connection foil 610 may be electroplated with acoherent metal 614, zinc, for example, which coats the exposed sectionof the anode connection foil 610 inside of the cathode pocket.Proceeding to 6F, the anode electrical collection masking layer 612 isremoved from the bottom of the anode connection foil 610 afterelectroplating.

FIGS. 7A-7F illustrate an alternate exemplary mode of processing thesteps illustrated in FIGS. 6A-6F. FIGS. 7A-7B may illustrate similarprocesses as depicted in FIGS. 6A-6B. The laminar structure may comprisetwo laminar construct release layers, 702 and 702 a, one layer on eitherend; two laminar construct adhesive layers, 704 and 704 a, locatedbetween the laminar construct release layers 702 and 702 a; and alaminar construct core 706, located between the two laminar constructadhesive layers 704 and 704 a. The laminar construct release layers andadhesive layers may be produced or purchased, such as a commerciallyavailable pressure-sensitive adhesive transfer tape with primary linerlayer. The laminar construct adhesive layers may be a polyvinylidenefluoride (PVDF) layer which may be approximately 1-3 millimeters inthickness and cap the laminar construct core 706. The laminar constructcore 706 may comprise a thermoplastic polymer resin such as polyethyleneterephthalate, which, for example, may be roughly 3 millimeters thick.Proceeding to FIG. 7B, a storage means, such as a cavity, for thecathode pocket 708, may be cut in the laminar construct by laser cuttingtreatment. In FIG. 7C, an anode connection foil 710 may be obtained anda protective masking layer 712 applied to one side. Next, at FIG. 7D,the anode connection foil 710 may be electroplated with a layer 714 of acoherent metal, for example, zinc. Proceeding to FIG. 7E, the laminarconstructs of FIGS. 7B and 7D may be combined to form a new laminarconstruct as depicted in FIG. 7E by adhering the construct of FIG. 7B tothe electroplated layer 714 of FIG. 7D. The release layer 702 a of FIG.7B may be removed in order to expose adhesive layer 704 a of FIG. 7B foradherence onto electroplated layer 714 of FIG. 7D. Proceeding next toFIG. 7F, the anode protective masking layer 712 may be removed from thebottom of the anode connection foil 710.

FIGS. 8A-8H illustrate exemplary implementations of energizationelements to a biocompatible laminar structure, which at times isreferred to as a laminar assembly or a laminate assembly herein, similarto, for example, those illustrated in FIGS. 6A-6F and 7A-7F. Proceedingto FIG. 8A, a hydrogel separator precursor mixture 820 may be depositedon the surface of the laminate assembly. In some examples, as depicted,the hydrogel precursor mixture 820 may be applied up a release layer802. Next, at FIG. 8B, the hydrogel separator precursor mixture 820 maybe squeegeed 850 into the cathode pocket while being cleaned off of therelease layer 802. The term “squeegeed” may generally refer to the useof a planarizing or scraping tool to rub across the surface and movefluid material over the surface and into cavities as they exist. Theprocess of squeegeeing may be performed by equipment similar to thevernacular “squeegee” type device or alternatively and planarizingdevice such as knife edges, razor edges and the like which may be madeof numerous materials as may be chemically consistent with the materialto be moved.

The processing depicted at FIG. 8B may be performed several times toensure coating of the cathode pocket, and increment the thickness ofresulting features. Next, at FIG. 8C, the hydrogel separator precursormixture may be allowed to dry in order to evaporate materials, which maytypically be solvents or diluents of various types, from the hydrogelseparator precursor mixture, and then the dispensed and appliedmaterials may be cured. It may be possible to repeat both of theprocesses depicted at FIG. 8B and FIG. 8C in combination in someexamples. In some examples, the hydrogel separator precursor mixture maybe cured by exposure to heat while in other examples the curing may beperformed by exposure to photon energy. In still further examples thecuring may involve both exposure to photon energy and to heat. There maybe numerous manners to cure the hydrogel separator precursor mixture.

The result of curing may be to form the hydrogel separator precursormaterial to the wall of the cavity as well as the surface region inproximity to an anode or cathode feature which in the present examplemay be an anode feature. Adherence of the material to the sidewalls ofthe cavity may be useful in the separation function of a separator. Theresult of curing may be to form an anhydrous polymerized precursormixture concentrate 822 which may be simply considered the separator ofthe cell. Proceeding to FIG. 8D, cathode slurry 830 may be depositedonto the surface of the laminar construct release layer 802. Next, atFIG. 8E the cathode slurry 830 may be squeegeed into the cathode pocketand onto the anhydrous polymerized precursor mixture concentrate 822.The cathode slurry may be moved to its desired location in the cavitywhile simultaneously being cleaned off to a large degree from thelaminar construct release layer 802. The process of FIG. 8E may beperformed several times to ensure coating of the cathode slurry 830 ontop of the anhydrous polymerized precursor mixture concentrate 822.Next, at FIG. 8F, the cathode slurry may be allowed to dry down to forman isolated cathode fill 832 on top of the anhydrous polymerizedprecursor mixture concentrate 822, filling in the remainder of thecathode pocket.

Proceeding to FIG. 8G, an electrolyte formulation 840 may be added on tothe isolated cathode fill 832 and allowed to hydrate the isolatedcathode fill 832 and the anhydrous polymerized precursor mixtureconcentrate 822. Next, at FIG. 8H, a cathode connection foil 816 may beadhered to the remaining laminar construct adhesive layer 804 byremoving the remaining laminar construct release layer 802 and pressingthe connection foil 816 in place. The resulting placement may result incovering the hydrated cathode fill 842 as well as establishingelectrical contact to the cathode fill 842 as a cathode currentcollector and connection means.

FIGS. 9A through 9C illustrate an alternative example of the resultinglaminate assembly from FIG. 7D. In FIG. 9A, the anode connection foil710 may be obtained and a protective masking layer 712 applied to oneside. The anode connection foil 710 may be plated with a layer 714 ofcoherent metal with, for example, zinc. In similar fashion as describedin the previous figures. Proceeding to FIG. 9B, a hydrogel separator 910may be applied without the use of the squeegee method illustrated inFIG. 8E. The hydrogel separator precursor mixture may be applied invarious manners, for example, a preformed film of the mixture may beadhered by physical adherence; alternatively, a diluted mixture of thehydrogel separator precursor mixture may be dispensed and then adjustedto a desired thickness by the processing of spin coating. Alternativelythe material may be applied by spray coating, or any other processingequivalent. Next, at FIG. 9C, processing is depicted to create a segmentof the hydrogel separator that may function as a containment around aseparator region. The processing may create a region that limits theflow, or diffusion, of materials such as electrolyte outside theinternal structure of the formed battery elements. Such a blockingfeature 920 of various types may therefore be formed. The blockingfeature, in some examples, may correspond to a highly crosslinked regionof the separator layer as may be formed in some examples by increasedexposure to photon energy in the desired region of the blocking feature920. In other examples, materials may be added to the hydrogel separatormaterial before it is cured to create regionally differentiated portionsthat upon curing become the blocking feature 920. In still furtherexamples, regions of the hydrogel separator material may be removedeither before or after curing by various techniques including, forexample, chemical etch of the layer with masking to define the regionalextent. The region of removed material may create a blocking feature inits own right or alternatively materially may be added back into thevoid to create a blocking feature. The processing of the impermeablesegment may occur through several methods including image outprocessing, increased crosslinking, heavy photodosing, back-filling, oromission of hydrogel adherence to create a void. In some examples, alaminate construct or assembly of the type depicted as the result of theprocessing in FIG. 9C may be formed without the blocking feature 920.

Polymerized Battery Element Separators

In some battery designs, the use of a discrete separator (as describedin a previous section) may be precluded due to a variety of reasons suchas the cost, the availability of materials, the quality of materials, orthe complexity of processing for some material options as non-limitingexamples. In such cases, a cast or form-in-place separator which isillustrated in the processes of FIGS. 8A-8H, for example, may providedesirable benefits. While starch or pasted separators have been usedcommercially with success in AA and other format Leclanche orzinc-carbon batteries, such separators may be unsuitable in some waysfor use in certain examples of laminar microbatteries. Particularattention may need to be paid to the uniformity and consistency ofgeometry for any separator used in the batteries of the presentinvention. Precise control over separator volume may be needed tofacilitate precise subsequent incorporation of known cathode volumes andsubsequent realization of consistent discharge capacities and cellperformance.

A method to achieve a uniform, mechanically robust form-in-placeseparator may be to use UV-curable hydrogel formulations. Numerouswater-permeable hydrogel formulations may be known in variousindustries, for example, the contact lens industry. An example of acommon hydrogel in the contact lens industry may bepoly(hydroxyethylmethacrylate) crosslinked gel, or simply pHEMA. Fornumerous applications of the present invention, pHEMA may possess manyattractive properties for use in Leclanche and zinc-carbon batteries.pHEMA typically may maintain a water content of approximately 30-40percent in the hydrated state while maintaining an elastic modulus ofabout 100 psi or greater. Furthermore, the modulus and water contentproperties of crosslinked hydrogels may be adjusted by one of skill inthe art by incorporating additional hydrophilic monomeric (e.g.methacrylic acid) or polymeric (e.g. polyvinylpyrrolidone) components.In this manner, the water content, or more specifically, the ionicpermeability of the hydrogel may be adjusted by formulation.

Of particular advantage in some examples, a castable and polymerizablehydrogel formulation may contain one or more diluents to facilitateprocessing. The diluent may be chosen to be volatile such that thecastable mixture may be squeegeed into a cavity, and then allowed asufficient drying time to remove the volatile solvent component. Afterdrying, a bulk photopolymerization may be initiated by exposure toactinic radiation of appropriate wavelength, such as blue UV light at420 nm, for the chosen photoinitiator, such as CGI 819. The volatilediluent may help to provide a desirable application viscosity so as tofacilitate casting a uniform layer of polymerizable material in thecavity. The volatile diluent may also provide beneficial surface tensionlowering effects, particularly in the case where strongly polar monomersare incorporated in the formulation. Another aspect that may beimportant to achieve the casting of a uniform layer of polymerizablematerial in the cavity may be the application viscosity. Common smallmolar mass reactive monomers typically do not have very highviscosities, which may be typically only a few centipoise. In an effortto provide beneficial viscosity control of the castable andpolymerizable separator material, a high molar mass polymeric componentknown to be compatible with the polymerizable material may be selectedfor incorporation into the formulation. Examples of high molar masspolymers which may be suitable for incorporation into exemplaryformulations may include polyvinylpyrrolidone and polyethylene oxide.

In some examples the castable, polymerizable separator may beadvantageously applied into a designed cavity, as previously described.In alternative examples, there may be no cavity at the time ofpolymerization. Instead, the castable, polymerizable separatorformulation may be coated onto an electrode-containing substrate, forexample, patterned zinc plated brass, and then subsequently exposed toactinic radiation using a photomask to selectively polymerize theseparator material in targeted areas. Unreacted separator material maythen be removed by exposure to appropriate rinsing solvents. In theseexamples, the separator material may be designated as aphoto-patternable separator.

Multiple Component Separator Formulations

The separator, useful according to examples of the present invention,may have a number of properties that may be important to its function.In some examples, the separator may desirably be formed in such a manneras to create a physical barrier such that layers on either side of theseparator do not physically contact one another. The layer may thereforehave an important characteristic of uniform thickness, since while athin layer may be desirable for numerous reasons, a void or gap freelayer may be essential. Additionally, the thin layer may desirably havea high permeability to allow for the free flow of ions. Also, theseparator requires optimal water uptake to optimize mechanicalproperties of the separator. Thus, the formulation may contain acrosslinking component, a hydrophilic polymer component, and a solventcomponent.

A crosslinker may be a monomer with two or more polymerizable doublebonds. Suitable crosslinkers may be compounds with two or morepolymerizable functional groups. Examples of suitable hydrophiliccrosslinkers may also include compounds having two or more polymerizablefunctional groups, as well as hydrophilic functional groups such aspolyether, amide or hydroxyl groups. Specific examples may includeTEGDMA (tetraethyleneglycol dimethacrylate), TrEGDMA (triethyleneglycoldimethacrylate), ethyleneglycol dimethacylate (EGDMA), ethylenediaminedimethyacrylamide, glycerol dimethacrylate and combinations thereof.

The amounts of crosslinker that may be used in some examples may range,e.g., from about 0.000415 to about 0.0156 mole per 100 grams of reactivecomponents in the reaction mixture. The amount of hydrophiliccrosslinker used may generally be about 0 to about 2 weight percent and,for example, from about 0.5 to about 2 weight percent. Hydrophilicpolymer components capable of increasing the viscosity of the reactivemixture and/or increasing the degree of hydrogen bonding with theslow-reacting hydrophilic monomer, such as high molecular weighthydrophilic polymers, may be desirable.

The high molecular weight hydrophilic polymers provide improvedwettability, and in some examples may improve wettability to theseparator of the present invention. In some non-limiting examples, itmay be believed that the high molecular weight hydrophilic polymers arehydrogen bond receivers which in aqueous environments, hydrogen bond towater, thus becoming effectively more hydrophilic. The absence of watermay facilitate the incorporation of the hydrophilic polymer in thereaction mixture. Aside from the specifically named high molecularweight hydrophilic polymers, it may be expected that any high molecularweight polymer will be useful in this invention provided that when saidpolymer is added to an exemplary silicone hydrogel formulation, thehydrophilic polymer (a) does not substantially phase separate from thereaction mixture and (b) imparts wettability to the resulting curedpolymer.

In some examples, the high molecular weight hydrophilic polymer may besoluble in the diluent at processing temperatures. Manufacturingprocesses which use water or water soluble diluents, such as isopropylalcohol (IPA), may be desirable examples due to their simplicity andreduced cost. In these examples, high molecular weight hydrophilicpolymers which are water soluble at processing temperatures may also bedesirable examples.

Examples of high molecular weight hydrophilic polymers may include butare not limited to polyamides, polylactones, polyimides, polylactams andfunctionalized polyamides, polylactones, polyimides, polylactams, suchas PVP and copolymers thereof, or alternatively, DMA functionalized bycopolymerizing DMA with a lesser molar amount of a hydroxyl-functionalmonomer such as HEMA, and then reacting the hydroxyl groups of theresulting copolymer with materials containing radical polymerizablegroups. High molecular weight hydrophilic polymers may include but arenot limited to poly-N-vinyl pyrrolidone, poly-N-vinyl-2-piperidone,poly-N-vinyl-2-caprolactam, poly-N-vinyl-3-methyl-2-caprolactam,poly-N-vinyl-3-methyl-2-piperidone, poly-N-vinyl-4-methyl-2-piperidone,poly-N-vinyl-4-methyl-2-caprolactam, poly-N-vinyl-3-ethyl-2-pyrrolidone,and poly-N-vinyl-4,5-dimethyl-2-pyrrolidone, polyvinylimidazole,poly-N—N-dimethylacrylamide, polyvinyl alcohol, polyacrylic acid,polyethylene oxide, poly 2 ethyl oxazoline, heparin polysaccharides,polysaccharides, mixtures and copolymers (including block or random,branched, multi-chain, comb-shaped or star-shaped) thereof wherepoly-N-vinylpyrrolidone (PVP) may be a desirable example where PVP hasbeen added to a hydrogel composition to form an interpenetrating networkwhich shows a low degree of surface friction and a low dehydration rate.

Additional components or additives, which may generally be known in theart, may also be included. Additives may include but are not limited toultra-violet absorbing compounds, photo-initiators such as CGI 819,reactive tints, antimicrobial compounds, pigments, photochromic, releaseagents, combinations thereof and the like.

The method associated with these types of separators may also includereceiving CGI 819; and then mixing with PVP, HEMA, EGDMA and IPA; andthen curing the resulting mixture with a heat source or an exposure tophotons. In some examples the exposure to photons may occur where thephotons' energy is consistent with a wavelength occurring in theultraviolet portion of the electromagnetic spectrum. Other methods ofinitiating polymerization generally performed in polymerizationreactions are within the scope of the present invention.

Current Collectors and Electrodes

In some examples of zinc carbon and Leclanche cells, the cathode currentcollector may be a sintered carbon rod. This type of material may facetechnical hurdles for thin electrochemical cells of the presentinvention. In some examples, printed carbon inks may be used in thinelectrochemical cells to replace a sintered carbon rod for the cathodecurrent collector, and in these examples, the resulting device may beformed without significant impairment to the resulting electrochemicalcell. Typically, said carbon inks may be applied directly to packagingmaterials which may comprise polymer films, or in some cases metalfoils. In the examples where the packaging film may be a metal foil, thecarbon ink may need to protect the underlying metal foil from chemicaldegradation and/or corrosion by the electrolyte. Furthermore, in theseexamples, the carbon ink current collector may need to provideelectrical conductivity from the inside of the electrochemical cell tothe outside of the electrochemical cell, implying sealing around orthrough the carbon ink. Due to the porous nature of carbon inks, thismay be not easily accomplished without significant challenges. Carboninks also may be applied in layers that have finite and relatively smallthickness, for example, 10 to 20 microns. In a thin electrochemical celldesign in which the total internal package thickness may only be about100 to 150 microns, the thickness of a carbon ink layer may take up asignificant fraction of the total internal volume of the electrochemicalcell, thereby negatively impacting electrical performance of the cell.Further, the thin nature of the overall battery and the currentcollector in particular may imply a small cross-sectional area for thecurrent collector. As resistance of a trace increases with trace lengthand decreases with cross-sectional area, there may be a direct tradeoffbetween current collector thickness and resistance. The bulk resistivityof carbon ink may be insufficient to meet the resistance requirement ofthin batteries. Inks filled with silver or other conductive metals mayalso be considered to decrease resistance and/or thickness, but they mayintroduce new challenges such as incompatibility with novelelectrolytes. In consideration of these factors, in some examples it maybe desirable to realize efficient and high performance thinelectrochemical cells of the present invention by utilizing a thin metalfoil as the current collector, or to apply a thin metal film to anunderlying polymer packaging layer to act as the current collector. Suchmetal foils may have significantly lower resistivity, thereby allowingthem to meet electrical resistance requirements with much less thicknessthan printed carbon inks.

In some examples, one or more of the top and/or bottom packaging layersmay serve as a substrate for a sputtered current collector metal ormetal stack. For example, 3M® Scotchpak 1109 backing may be metallizedusing physical vapor deposition (PVD) of one or more metallic layersuseful as a current collector for a cathode. Examplary metal stacksuseful as cathode current collectors may be Ti—W (titanium-tungsten)adhesion layers and Ti (titanium) conductor layers. Exemplary metalstacks useful as anode current collectors may be Ti—W adhesion layers,Au (gold) conductor layers, and In (indium) deposition layers. Thethickness of the PVD layers may be less than 500 nm in total. Ifmultiple layers of metals are used, the electrochemical and barrierproperties may need to be compatible with the battery. For example,copper may be electroplated on top of a seed layer to grow a thick layerof conductor. Additional layers may be plated upon the copper. However,copper may be electrochemically incompatible with certain electrolytesespecially in the presence of zinc. Accordingly, if copper is used as alayer in the battery, it may need to be sufficiently isolated from thebattery electrolyte. Alternatively, copper may be excluded or anothermetal substituted.

In some other examples, top and/or bottom packaging foils may alsofunction as current collectors. For example, a 25 micron brass foil maybe useful as an anode current collector for a zinc anode. The brass foilmay be optionally electroplated with indium prior to electroplating withzinc. In one example, cathode current collector packaging foils maycomprise titanium foil, Hastelloy C-276 foil, chromium foil, and/ortantalum foil. In certain designs, one or more packaging foils may befine blanked, embossed, etched, textured, laser machined, or otherwiseprocessed to provide desirable form, surface roughness, and/or geometryto the final cell packaging.

Anode and Anode Corrosion Inhibitors

The anode for the laminar battery of the present invention may, forexample, comprise zinc. In traditional zinc carbon batteries, a zincanode may take the physical form of a can in which the contents of theelectrochemical cell may be contained. For the battery of the presentinvention, a zinc can may be an example but there may be other physicalforms of zinc that may provide desirable to realize ultra-small batterydesigns.

Electroplated zinc may have examples of use in a number of industries,for example, for the protective or aesthetic coating of metal parts. Insome examples, electroplated zinc may be used to form thin and conformalanodes useful for batteries of the present invention. Furthermore, theelectroplated zinc may be patterned in seemingly endless configurations,depending on the design intent. A facile means for patterningelectroplated zinc may be processing with the use of a photomask or aphysical mask. A plating mask may be fabricated by a variety ofapproaches. One approach may be by using a photomask. In these examples,a photoresist may be applied to a conductive substrate, the substrate onwhich zinc may subsequently be plated. The desired plating pattern maybe then projected to the photoresist by means of a photomask, therebycausing curing of selected areas of photoresist. The uncured photoresistmay then be removed with appropriate solvent and cleaning techniques.The result may be a patterned area of conductive material that mayreceive an electroplated zinc treatment. While this method may providebenefit to the shape or design of the zinc to be plated, the approachmay require use of available photopatternable materials, which may haveconstrained properties to the overall cell package construction.Consequently, new and novel methods for patterning zinc may be requiredto realize some designs of thin microbatteries of the present invention.

An alternative means of patterning zinc anodes may be by means of aphysical mask application. A physical mask may be made by cuttingdesirable apertures in a film having desirable barrier and/or packagingproperties. Additionally, the film may have pressure sensitive adhesiveapplied to one or both sides. Finally, the film may have protectiverelease liners applied to one or both adhesives. The release liner mayserve the dual purpose of protecting the adhesive during aperturecutting and protecting the adhesive during specific processing steps ofassembling the electrochemical cell, specifically the cathode fillingstep, described in following description. In some examples, a zinc maskmay comprise a PET film of approximately 100 microns thickness to whicha pressure sensitive adhesive may be applied to both sides in a layerthickness of approximately 10-20 microns. Both PSA layers may be coveredby a PET release film which may have a low surface energy surfacetreatment, and may have an approximate thickness of 50 microns. In theseexamples, the multi-layer zinc mask may comprise PSA and PET film. PETfilms and PET/PSA zinc mask constructs as described herein may bedesirably processed with precision nanosecond laser micromachiningequipment, such as, Oxford Lasers E-Series laser micromachiningworkstation, to create ultra-precise apertures in the mask to facilitatelater plating. In essence, once the zinc mask has been fabricated, oneside of the release liner may be removed, and the mask with aperturesmay be laminated to the anode current collector and/or anode-sidepackaging film/foil. In this manner, the PSA creates a seal at theinside edges of the apertures, facilitating clean and precise masking ofthe zinc during electroplating.

The zinc mask may be placed and then electroplating of one or moremetallic materials may be performed. In some examples, zinc may beelectroplated directly onto an electrochemically compatible anodecurrent collector foil such as brass. In alternate design examples wherethe anode side packaging comprises a polymer film or multi-layer polymerfilm upon which seed metallization has been applied, zinc, and/or theplating solutions used for depositing zinc, may not be chemicallycompatible with the underlying seed metallization. Manifestations oflack of compatibility may include film cracking, corrosion, and/orexacerbated H₂ evolution upon contact with cell electrolyte. In such acase, additional metals may be applied to the seed metal to affectbetter overall chemical compatibility in the system. One metal that mayfind particular utility in electrochemical cell constructions may beindium. Indium may be widely used as an alloying agent in battery gradezinc with its primary function being to provide an anti-corrosionproperty to the zinc in the presence of electrolyte. In some examples,indium may be successfully deposited on various seed metallizations suchas Ti—W and Au. Resulting films of 1-3 microns of indium on said seedmetallization layers may be low-stress and adherent. In this manner, theanode-side packaging film and attached current collector having anindium top layer may be conformable and durable. In some examples, itmay be possible to deposit zinc on an indium-treated surface, theresulting deposit may be very non-uniform and nodular. This effect mayoccur at lower current density settings, for example, 20 ASF. As viewedunder a microscope, nodules of zinc may be observed to form on theunderlying smooth indium deposit. In certain electrochemical celldesigns, the vertical space allowance for the zinc anode layer may be upto about 5-10 microns maximum, but in some examples, lower currentdensities may be used for zinc plating, and the resulting nodulargrowths may grow taller than the maximum anode vertical allowance. Itmay be that the nodular zinc growth stems from a combination of the highoverpotential of indium and the presence of an oxide layer of indium.

In some examples, higher current density DC plating may overcome therelatively large nodular growth patterns of zinc on indium surfaces. Forexample, 100 ASF plating conditions may result in nodular zinc, but thesize of the zinc nodules may be drastically reduced compared to 20 ASFplating conditions. Furthermore, the number of nodules may be vastlygreater under 100 ASF plating conditions. The resulting zinc film mayultimately coalesce to a more or less uniform layer with only someresidual feature of nodular growth while meeting the vertical spaceallowance of about 5-10 microns.

An added benefit of indium in the electrochemical cell may be reductionof H₂ formation, which may be a slow process that occurs in aqueouselectrochemical cells containing zinc. The indium may be beneficiallyapplied to one or more of the anode current collector, the anode itselfas a co-plated alloying component, or as a surface coating on theelectroplated zinc. For the latter case, indium surface coatings may bedesirably applied in-situ by way of an electrolyte additive such asindium trichloride or indium acetate. When such additives may be addedto the electrolyte in small concentrations, indium may spontaneouslyplate on exposed zinc surfaces as well as portions of exposed anodecurrent collector.

Zinc and similar anodes commonly used in commercial primary batteries istypically found in sheet, rod, and paste forms. The anode of aminiature, biocompatible battery may be of similar form, e.g. thin foil,or may be plated as previously mentioned. The properties of this anodemay differ significantly from those in existing batteries, for example,because of differences in contaminants or surface finish attributed tomachining and plating processes. Accordingly, the electrodes andelectrolyte may require special engineering to meet capacity, impedance,and shelf life requirements. For example, special plating processparameters, plating bath composition, surface treatment, and electrolytecomposition may be needed to optimize electrode performance.

Cathode Mixture

There may be numerous cathode chemistry mixtures that may be consistentwith the concepts of the present invention. In some examples, a cathodemixture, which may be a term for a chemical formulation used to form abattery's cathode, may be applied as a paste, gel, suspension, orslurry, and may comprise a transition metal oxide such as manganesedioxide, some form of conductive additive which, for example, may be aform of conductive powder such as carbon black or graphite, and awater-soluble polymer such as polyvinylpyrrolidone (PVP) or some otherbinder additive. In some examples, other components may be included suchas one or more of binders, electrolyte salts, corrosion inhibitors,water or other solvents, surfactants, rheology modifiers, and otherconductive additives, such as, conductive polymers. Once formulated andappropriately mixed, the cathode mixture may have a desirable rheologythat allows it to either be dispensed onto desired portions of theseparator and/or cathode current collector, or squeegeed through ascreen or stencil in a similar manner. In some examples, the cathodemixture may be dried before being used in later cell assembly steps,while in other examples, the cathode may contain some or all of theelectrolyte components, and may only be partially dried to a selectedmoisture content.

The transition metal oxide may, for example, be manganese dioxide. Themanganese dioxide which may be used in the cathode mixture may be, forexample, electrolytic manganese dioxide (EMD) due to the beneficialadditional specific energy that this type of manganese dioxide providesrelative to other forms, such as natural manganese dioxide (NMD) orchemical manganese dioxide (CMD). Furthermore, the EMD useful inbatteries of the present invention may need to have a particle size andparticle size distribution that may be conducive to the formation ofdepositable or printable cathode mixture pastes/slurries. Specifically,the EMD may be processed to remove significant large particulatecomponents that may be considered large relative to other features suchas battery internal dimensions, separator thicknesses, dispense tipdiameters, stencil opening sizes, or screen mesh sizes. Particle sizeoptimization may also be used to improve performance of the battery, forexample, internal impedance and discharge capacity.

Milling is the reduction of solid materials from one average particlesize to a smaller average particle size, by crushing, grinding, cutting,vibrating, or other processes. Milling may also be used to free usefulmaterials from matrix materials in which they may be embedded, and toconcentrate minerals. A mill is a device that breaks solid materialsinto smaller pieces by grinding, crushing, or cutting. There may beseveral means for milling and many types of materials processed in them.Such means of milling may include: ball mill, bead mill, mortar andpestle, roller press, and jet mill among other milling alternatives. Oneexample of milling may be jet milling. After the milling, the state ofthe solid is changed, for example, the particle size, the particle sizedisposition and the particle shape. Aggregate milling processes may alsobe used to remove or separate contamination or moisture from aggregateto produce “dry fills” prior to transport or structural filling. Someequipment may combine various techniques to sort a solid material into amixture of particles whose size is bounded by both a minimum and maximumparticle size. Such processing may be referred to as “classifiers” or“classification.”

Milling may be one aspect of cathode mixture production for uniformparticle size distribution of the cathode mixture ingredients. Uniformparticle size in a cathode mixture may assist in viscosity, rheology,electroconductivity, and other properties of a cathode. Milling mayassist these properties by controlling agglomeration, or a masscollection, of the cathode mixture ingredients. Agglomeration—theclustering of disparate elements, which in the case of the cathodemixture, may be carbon allotropes and transition metal oxides—maynegatively affect the filling process by leaving voids in the desiredcathode cavity as illustrated in FIG. 11.

Also, filtration may be another important step for the removal ofagglomerated or unwanted particles. Unwanted particles may includeover-sized particles, contaminates, or other particles not explicitlyaccounted for in the preparation process. Filtration may be accomplishedby means such as filter-paper filtration, vacuum filtration,chromatography, microfiltration, and other means of filtration.

In some examples, EMD may have an average particle size of 7 micronswith a large particle content that may contain particulates up to about70 microns. In alternative examples, the EMD may be sieved, furthermilled, or otherwise separated or processed to limit large particulatecontent to below a certain threshold, for example, 25 microns orsmaller.

The cathode may also comprise silver dioxide or nickel oxyhydroxide.Such materials may offer increased capacity and less decrease in loadedvoltage during discharge relative to manganese dioxide, both desirableproperties in a battery. Batteries based on these cathodes may havecurrent examples present in industry and literature. A novelmicrobattery utilizing a silver dioxide cathode may include abiocompatible electrolyte, for example, one comprising zinc chlorideand/or ammonium chloride instead of potassium hydroxide.

Some examples of the cathode mixture may include a polymeric binder. Thebinder may serve a number of functions in the cathode mixture. Theprimary function of the binder may be to create a sufficientinter-particle electrical network between EMD particles and carbonparticles. A secondary function of the binder may be to facilitatemechanical adhesion and electrical contact to the cathode currentcollector. A third function of the binder may be to influence therheological properties of the cathode mixture for advantageousdispensing and/or stenciling/screening. Still, a fourth function of thebinder may be to enhance the electrolyte uptake and distribution withinthe cathode.

The choice of the binder polymer as well as the amount to be used may bebeneficial to the function of the cathode in the electrochemical cell ofthe present invention. If the binder polymer is too soluble in theelectrolyte to be used, then the primary function of thebinder—electrical continuity—may be drastically impacted to the point ofcell non-functionality. On the contrary, if the binder polymer isinsoluble in the electrolyte to be used, portions of EMD may beionically insulated from the electrolyte, resulting in diminished cellperformance such as reduced capacity, lower open circuit voltage, and/orincreased internal resistance.

The binder may be hydrophobic; it may also be hydrophilic. Examples ofbinder polymers useful for the present invention comprise PVP,polyisobutylene (PIB), rubbery triblock copolymers comprising styreneend blocks such as those manufactured by Kraton Polymers,styrene-butadiene latex block copolymers, polyacrylic acid,hydroxyethylcellulose, carboxymethylcellulose, fluorocarbon solids suchas polytetrafluoroethylene, among others.

A solvent may be one component of the cathode mixture. A solvent may beuseful in wetting the cathode mixture, which may assist in the particledistribution of the mixture. One example of a solvent may be toluene.Also, a surfactant may be useful in wetting, and thus distribution, ofthe cathode mixture. One example of a surfactant may be a detergent,such as Triton™ QS-44. Triton™ QS-44 may assist in the dissociation ofaggregated ingredients in the cathode mixture, allowing for a moreuniform distribution of the cathode mixture ingredients.

A conductive carbon may typically be used in the production of acathode. Carbon is capable of forming many allotropes, or differentstructural modifications. Different carbon allotropes have differentphysical properties allowing for variation in electroconductivity. Forexample, the “springiness” of carbon black may help with adherence of acathode mixture to a current collector. However, in energizationelements requiring relatively low amounts of energy, these variations inelectroconductivity may be less important than other favorableproperties such as density, particle size, heat conductivity, andrelative uniformity, among other properties. Examples of carbonallotropes include: diamond, graphite, graphene, amorphous carbon(informally called carbon black), buckminsterfullerenes, glassy carbon(also called vitreous carbon), carbon aerogels, and other possible formsof carbon capable of conducting electricity. One example of a carbonallotrope may be graphite.

One example of a completed cathode mixture formulation may be given inthe table below:

Relative Formulation Example weight 80:20 JMEMD/KS6 4.900 PIB B10 (from20% 0.100 solution) toluene 2.980 Total 7.980where PIB is polyisobutylene, JMEMD is jet milled manganese dioxide, KS6is a graphite produced by Timcal, and PIB B10 is polyisobutylene with amolecular weight grade of B10.

Once the cathode mixture has been formulated and processed, the mixturemay be dispensed, applied, and/or stored onto a surface such as thehydrogel separator, or the cathode current collector, or into a volumesuch as the cavity in the laminar structure. Filing onto a surface mayresult in a volume being filled over time. In order to apply, dispense,and/or store the mixture, a certain rheology may be desired to optimizethe dispensing, applying, and/or storing process. For example, a lessviscous rheology may allow for better filling of the cavity while at thesame time possibly sacrificing particle distribution. A more viscousrheology may allow for optimized particle distribution, while possiblydecreasing the ability to fill the cavity and possibly losingelectroconductivity.

For example, FIGS. 10A-10F illustrate examples of optimized andnon-optimized dispensing or application into a cavity. FIG. 10A shows anexample of a cavity optimally filled with the cathode mixture afterapplication, dispensing, and/or storing. FIG. 10B shows an example of acavity with insufficient filling in the bottom left quadrant 1002, whichmay be a direct result of undesirable cathode mixture rheology. FIG. 10Cshows an example of a cavity with insufficient filling in the top rightquadrant 1004, which may be a direct result of undesirable cathodemixture rheology. FIGS. 10D and 10E show examples of a cavity withinsufficient filling in the middle 1006 or bottom 1008 of the cavity,which may be a bubble caused by a direct result of undesirable cathodemixture rheology. FIG. 10F shows an example of a cavity withinsufficient filling towards the top 1010 of the cavity, which may be adirect result of undesirable cathode mixture rheology. The exemplarydefects illustrated in FIGS. 10B-10F may result in several batteryissues, for example, reduced capacity, increased internal resistance,and degraded reliability.

Further, in FIG. 11, agglomeration 1102 may occur as a result ofundesirable cathode mixture rheology. Agglomeration may result indecreased performance of the cathode mixture, for example, decreaseddischarge capacity and increased internal resistance.

In one example, the cathode mixture may resemble a peanut-butter likeconsistency optimized for squeegee filling the laminar construct cavitywhile maintaining electroconductivity. In another example, the mixturemay be viscous enough to be printed into the cavity. While in yetanother example, the cathode mixture may be dried, placed, and stored inthe cavity.

Cathode Manufacturing

Cathode slurry chemistry may play a role in determining cathode slurryperformance. Additives for cathode slurries may consist of oxidizers,buffers, stabilizers, surfactants, passivating agents, complexingagents, corrosion inhibitors, or other agents for imparting selectivityto various surfaces. In addition, cathode slurries may contain additivesfor colloidal stability and/or buffers to withstand pH shock. Developinggood cathode slurry may require balancing the combinations of these andother additives so that they give the required performance as well asthe requisite physical and chemical characteristics.

Particle size may affect cathode slurry performance. Particle sizedistribution may be measured by, for example, laser diffraction, dynamiclight scattering, hydrodynamic fractionation, sedimentation, andacoustic methods. In some examples, the estimation of particle size maygenerate relative values rather than absolute values which may depend onthe measurement technique used. Process control of the slurry materialcharacteristics may nonetheless be effective based on the control ofrelative values within process control specifications.

Cathode slurries may consist of a liquid phase, such as a solvent, and asolid phase, such as oxidizers, surfactants, complexing agents, buffers,and/or other additives. The two components may be stored separately forreasons of physical or chemical stability. The number of components inthe cathode slurry may affect the manufacturing process. Robustness ofthe manufacturing process may depend on the minimized variance of themix ratio of the components particularly as the number of componentsincrease. On the other hand, there may be important drivers forincluding additional components. In a non-limiting example, it may beuseful to include a biocide as a component of the formulation of acathode slurry for both biocompatibility and longevity of slurry potlife (the life of the cathode slurry after the components are mixed). Insuch examples, the addition of the extra biocide component may notrelate to meaningful performance of resulting batteries, but may beimportant none the less for the reasons stated. Control over the mixratio of all components in a slurry mixture may aid in overall controlin complex formulations. In other examples, multiple component cathodeslurries may have a limited pot life. For some complex formulations,there may be changes that occur to the slurry over time after it ismixed by effects such as evaporation or absorption or desorption ofgasses from the mixture. In such examples, control over dilution and pHmay need to be taken into consideration when adding more components.

Colloidal stability of the cathode slurry may also be an importantmanufacturing consideration. For example, cathode slurry where thecolloidal nature is unstable may have more particles settling out of themixture. Therefore, unstable cathode slurries may need more frequentchanges of filters and may need special mixing equipment. If aformulation is optimized as much as practical and has a degree ofcolloidal instability it may require significant monitoring of variousprocess parameters to ensure the formulation remains in a desiredspecification range. As part of reaching a degree of colloidalstability, the formulation may include surfactants to alter surfacecharacteristics of some solids in the slurry. In other examples, ambientcontrols may be used to improve colloidal stability. For example, thetemperature of the slurry mixture and the control of that temperaturewithin a range may improve stability. In some examples therefore,formulations for cathode slurries may require ideal temperature rangesduring manufacturing which may include the storage, mixing anddistribution aspects as well as the battery processing aspectsthemselves.

The nature and composition of cathode slurry may have an effect onmanufacturability. In large scale manufacturing, the cathode slurry maybe produced and delivered by means of a cathode slurry distributionsystem (cSDS), as illustrated in an exemplary fashion in FIG. 12. InFIG. 12, all of the reagents 1200 for the cathode slurry may be heldseparately in individual holding cells. This may include individualsolid phase reagents 1202, 1204, 1208 and individual liquid phasereagents 1206. In one example, a first solid phase component may be Jetmilled electrolytic manganese dioxide (JMEMD); a second solid phasereagent may be carbon black; a third solid phase component may bepolyisobutylene (PIB); and a first liquid phase component may betoluene. These reagents may be purchased by a commercial vendor orproduced in-house.

Regardless of the origin of the reagents, a level of reagent processing1210 must occur. Reagent processing may include sieving 1212, 1214,1218, filtering 1216, or both. In one example, JMEMD may be sieved 1212to an optimal particle size; carbon black may be sieved 1214 to anoptimal particle size; PIB may be sieved 1218 to an optimal particlesize; and toluene may be filtered 1216 to remove any contaminates orunwanted particles. Means of sieving may include using sieving toolssuch as a: basket strainer, Y strainer, bell mouth strainer, foot valvestrainer, metal sifter, colander, graduated sieves, mesh strainer, andother devices used for particle size distribution. Filtering may beachieved by using filtering means such as a: filter paper,microfiltration, ultrafiltration, nanofiltration, chromatography, andother forms of filtration.

Once the reagents have been processed, they may be ready for transfer toreagent pre-mixing 1220. Depending on the desired type of cathodeslurry, the reagents may be pre-mixed in a variety of combinations. Oneexample may be pre-mixing two solid phases together in one cell, andpre-mixing one solid phase with one liquid phase in another cell. Forexample, JMEMD and carbon black may be pre-mixed together in one solidphase pre-mixture 1222 and toluene and PIB may be pre-mixed together ina different liquid phase pre-mixture 1224.

After pre-mixing, the cSDS may incorporate added functionality thatallows for monitoring and maintaining cathode slurry quality 1230, whichmay be important for maximizing yield. Each pre-mixing cell may requiredistinct quality control measures, 1232 and 1234, optimized for thepre-mixing phase it is receiving. Commonly measured parameters mayinclude pH, specific gravity, and particle size distribution andoxidizer concentration. Further, pumps, valves, fittings, and othercomponents may have an effect on cathode slurry properties. In oneexample, the solids phase pre-mixture 1222 may require particle sizedistribution quality control 1232 by appropriate inspection.

To monitor the behavior of cathode slurry, both physical and chemicalproperties may be measured. Measurements of physical properties mayinclude pH, weight per gallon, specific gravity, conductivity, andpercent solids. Viscosity may be measured by using a BROOKFIELDviscometer, which may be useful given that cathode slurries may behavein a Newtonian manner (viscosity is independent of shear rate). However,some formulations of slurries useful for cathode formation may result inslurries which may be characterized as non-Newtonian cathode slurries.In examples of non-Newtonian slurry dynamics, the viscosity may bemeasured as a function of shear rate using a shear rate or stresscontrolled rheometer. One example of a viscosity useful for applicationsof cathode slurry, according to the examples of the present disclosurefor filling of cavities, may be approximately 250,000 Pa·s. Viscositymay be an important metric that may need to be measured in the cSDS loopas well as during distribution as part of a quality control system tominimize variability in the properties of slurry that gets deliveredduring the manufacturing of biocompatible batteries.

After quality control, the solid phases and liquid phases may be mixedtogether 1240 to form a slurry mixture 1242. The slurry mixture may becontained in a cell where constant mixing is taking place in order tokeep the slurry phases from separating. This may be accomplished with anindustrial-size mixing vessel.

Once slurry mixing has been accomplished, another filtration and qualitycontrol step 1244 may be performed. The cathode slurry that passes thisquality control step may proceed to slurry storage 1250. Slurry storagemay be used for high volume manufacturing to keep up with volumerequirements. The cathode slurry mixture contained in the storagecontainer may need to be re-circulated 1253 back into slurry mixing 1242in order to re-mix the solid and liquid phases back into a slurrymixture. This step may be used because the slurry maintained intransport lines throughout the cSDS may require re-mixing as well.Cathode slurry mixture re-circulation may be implemented by means ofdouble diaphragm or bellow pumps, as well as pressure/pressure orvacuum/pressure methods. Gear, vane, or centrifugal pumps may generatehigh shear that may cause aggregation in the system. As an example, aminimum flow rate of 1 m/s may be used for cathode slurryre-circulation. Cathode slurry mixture in slurry storage 1252 may thenproceed to a filtration and quality control step 1254 before proceedingto slurry distribution/filling 1260.

Slurry distribution/filling may require obtaining a laminar structurewith a cavity 1262. Once the laminar structure with a cavity 1262 isobtained, the cathode slurry mixture may be deposited onto a desiredsurface, for example, the laminar structure. Distribution/filling may beaccomplished by, for example, the squeegee method as illustrated in FIG.8. After slurry distribution/filling, drying steps 1270 may be performedincluding drying or evaporating 1272 excess liquid phase such astoluene.

Numerous steps have been described in reference to the present inventionin an exemplary manner. It may be understood that various modifications,additions, deletions, and changes of such nature are possible within thescope herein. As an example, the various materials may have pre- orpost-treatments performed on them additionally to what has beendescribed.

Handling of cathode slurry in a cSDS may be a delicate task and care maybe taken to ensure that the cathode slurry is not damaged. This may meannot subjecting the cathode slurry to shear that is too high (may causeaggregation) or too low (may cause settling), keeping the headspace inthe tanks moist, and performing regular maintenance on the system.Optimization of the cSDS system may be needed to reduce aggregation andminimize process variation.

Battery Architecture and Fabrication

Battery architecture and fabrication technology may be closelyintertwined. As has been discussed in earlier sections of the presentinvention, a battery has the following elements:

cathode, anode, separator, electrolyte, cathode current collector, anodecurrent collector, and packaging. Clever design may try to combine theseelements in easy to fabricate subassemblies. In other examples,optimized design may have dual-use components, such as, using a metalpackage to double as a current collector. From a relative volume andthickness standpoint, these elements may be nearly all the same volume,except for the cathode. In some examples, the electrochemical system mayrequire about two (2) to ten (10) times the volume of cathode as anodedue to significant differences in mechanical density, energy density,discharge efficiency, material purity, and the presence of binders,fillers, and conductive agents. In these examples, the relative scale ofthe various components may be approximated in the following thicknessesof the elements: Anode current collector=1 μm; Cathode currentcollector=1 μm; Electrolyte=interstitial liquid (effectively 0 μm);Separator=as thin or thick as desired where the planned maximalthickness may be approximately 15 μm; Anode=5 μm; and the Cathode=50 μm.For these examples of elements the packaging needed to providesufficient protection to maintain battery chemistry in use environmentsmay have a planned maximal thickness of approximately 50 μm.

In some examples, which may be fundamentally different from large,prismatic constructs such as cylindrical or rectangular forms and whichmay be different than wafer-based solid state construct, such examplesmay assume a “pouch”-like construct, using webs or sheets fabricatedinto various configurations, with battery elements arranged inside. Thecontainment may have two films or one film folded over onto the otherside either configuration of which may form two roughly planar surfaces,which may be then sealed on the perimeter to form a container. Thisthin-but-wide form factor may make battery elements themselves thin andwide. Furthermore, these examples may be suitable for applicationthrough coating, gravure printing, screen printing, sputtering, or othersimilar fabrication technology.

There may be numerous arrangements of the internal components, such asthe anode, separator and cathode, in these “pouch-like” battery exampleswith thin-but-wide form factor. Within the enclosed region formed by thetwo films, these basic elements may be either “co-planar” that isside-by-side on the same plane or “co-facial” which may be face-to-faceon opposite planes. In the co-planar arrangement, the anode, separator,and cathode may be deposited on the same surface. For the co-facialarrangement, the anode may be deposited on surface-1, the cathode may bedeposited on surface-2, and the separator may be placed between the two,either deposited on one of the sides, or inserted as its own separateelement.

Another type of example may be classified as laminate assembly, whichmay involve using films, either in a web or sheet form, to build up abattery layer by layer. Sheets may be bonded to each other usingadhesives, such as pressure-sensitive adhesives, thermally activatedadhesives, or chemical reaction-based adhesives. In some examples thesheets may be bonded by welding techniques such as thermal welding,ultrasonic welding and the like. Sheets may lend themselves to standardindustry practices as roll-to-roll (R2R), or sheet-to-sheet assembly. Asindicted earlier, an interior volume for cathode may need to besubstantially larger than the other active elements in the battery. Muchof a battery construct may have to create the space of this cathodematerial, and support it from migration during flexing of the battery.Another portion of the battery construct that may consume significantportions of the thickness budget may be the separator material. In someexamples, a sheet form of separator may create an advantageous solutionfor laminate processing. In other examples, the separator may be formedby dispensing hydrogel material into a layer to act as the separator.

In these laminate battery assembly examples, the forming product mayhave an anode sheet, which may be a combination of a package layer andan anode current collector, as well as substrate for the anode layer.The forming product may also have an optional separator spacer sheet, acathode spacer sheet, and a cathode sheet. The cathode sheet may be acombination of a package layer and a cathode current collector layer.

Intimate contact between electrodes and current collectors is ofcritical importance for reducing impedance and increasing dischargecapacity. If portions of the electrode are not in contact with thecurrent collector, resistance may increase since conductivity is thenthrough the electrode (typically less conductive than the currentcollector) or a portion of the electrode may become totallydisconnected. In coin cell and cylindrical batteries, intimacy isrealized with mechanical force to crimp the can, pack paste into a can,or through similar means. Wave washers or similar springs are used incommercial cells to maintain force within the battery; however, thesemay add to the overall thickness of a miniature battery. In typicalpatch batteries, a separator may be saturated in electrolyte, placedacross the electrodes, and pressed down by the external packaging. In alaminar, cofacial battery there are several methods to increaseelectrode intimacy. The anode may be plated directly onto the currentcollector rather than using a paste. This process inherently results ina high level of intimacy and conductivity. The cathode, however, istypically a paste. Although binder material present in the cathode pastemay provide adhesion and cohesion, mechanical pressure may be needed toensure the cathode paste remains in contact with the cathode currentcollector. This may be especially important as the package is flexed andthe battery ages and discharges, for example, as moisture leaves thepackage through thin and small seals. Compression of the cathode may beachieved in the laminar, cofacial battery by introducing a compliantseparator and/or electrolyte between the anode and cathode. A gelelectrolyte or hydrogel separator, for example, may compress on assemblyand not simply run out of the battery as a liquid electrolyte might.Once the battery is sealed, the electrolyte and/or separator may thenpush back against the cathode. An embossing step may be performed afterassembly of the laminar stack, introducing compression into the stack.

The cathode mixture for use in biocompatible batteries may be used inbiocompatible devices such as, for example, implantable electronicdevices, such as pacemakers and micro-energy harvesters, electronicpills for monitoring and/or testing a biological function, surgicaldevices with active components, ophthalmic devices, microsized pumps,defibrillators, stents, and the like.

Specific examples have been described to illustrate sample embodimentsfor the cathode mixture for use in biocompatible batteries. Theseexamples are for said illustration and are not intended to limit thescope of the claims in any manner. Accordingly, the description isintended to embrace all examples that may be apparent to those skilledin the art.

What is claimed is:
 1. A method for manufacturing a cathode slurry foruse in a biocompatible battery comprising the steps of: mixing one ormore of a liquid phase pre-mixture with one or more of a solid phasepre-mixture into a cathode slurry mixture; obtaining a laminar structurewherein the laminar structure has a volume removed to form a cavity;filtering the cathode slurry mixture; and distributing the cathodeslurry mixture into the cavity of the laminar structure to form abiocompatible cathode for use in a biocompatible battery.
 2. The methodof claim 1 further comprising checking a quality of the solid phasepre-mixture and the liquid phase pre-mixture.
 3. The method of claim 1further comprising storing and recirculating the cathode slurry mixtureafter filtering the cathode slurry mixture.
 4. The method of claim 1further comprising drying the cathode slurry mixture.
 5. The method ofclaim 1 wherein the liquid phase pre-mixture comprises one or morereagents wherein at least one reagent is a liquid phase reagent.
 6. Themethod of claim 5 further comprising filtering the liquid phasereagents.
 7. The method of claim 5 wherein one liquid phase reagentcomprises a solvent.
 8. The method of claim 7 wherein the solventcomprises toluene.
 9. The method of claim 1 wherein the solid phasepre-mixture comprises one or more solid phase reagents.
 10. The methodof claim 9 further comprising sieving the solid phase reagents to auniform particle size.
 11. The method of claim 9 wherein the solid phasereagent comprises a jet milled electrolytic manganese dioxide.
 12. Themethod of claim 9 wherein one solid phase pre-mixture comprises atransition metal oxide.
 13. The method of claim 12 wherein thetransition metal oxide comprises manganese dioxide.
 14. The method ofclaim 9 wherein one solid phase reagent comprises a carbon allotrope.15. The method of claim 14 wherein the carbon allotrope comprisesgraphite.
 16. The method of claim 15 wherein the graphite comprisescarbon black.
 17. The method of claim 5 wherein the liquid phasepre-mixture comprises a hydrophobic binder.
 18. The method of claim 17wherein the hydrophobic binder comprises polyisobutylene (PIB).
 19. Themethod of claim 17 wherein the hydrophobic binder comprises afluorocarbon solid.
 20. The method of claim 19 wherein the fluorocarbonsolid comprises polytetrafluoroethylene (PTFE).
 21. A method formanufacturing a biocompatible cathode for use in a biocompatible batterycomprising the steps of: obtaining toluene, manganese dioxide, carbonblack, and polyisobutylene; filtering toluene; sieving manganesedioxide; sieving carbon black; sieving polyisobutylene; mixing thetoluene and the polyisobutylene into a liquid phase pre-mixture; mixingthe manganese dioxide and carbon black into a solid phase pre-mixture;checking a quality of both the solid and liquid phase pre-mixturesmixing the solid phase pre-mixture and liquid phase pre-mixture into acathode slurry mixture; filtering the cathode slurry mixture; storingthe cathode slurry mixture; recirculating the cathode slurry mixture;obtaining a laminar structure wherein the laminar structure has a volumeremoved to form a cavity; filtering the stored cathode slurry mixture;distributing the filtered cathode slurry mixture into the cavity of thelaminar structure; and drying the cathode slurry mixture to form abiocompatible cathode for use in a biocompatible battery.
 22. A methodfor manufacturing a cathode slurry for use in a biomedical devicecomprising comprising the steps of: mixing one or more of a liquid phasepre-mixture with one or more of a solid phase pre-mixture into a cathodeslurry mixture; obtaining a laminar structure wherein the laminarstructure has a volume removed to form a cavity; filtering the cathodeslurry mixture; and distributing the cathode slurry mixture into thecavity of the laminar structure forming the cathode slurry for use in abiomedical device; wherein the biomedical device comprises an insertdevice comprising: an electroactive element responsive to a controllingvoltage signal; a biocompatible battery; wherein the biocompatiblebattery comprises: a first and second electrode; an anode; a separator;a laminar structure, wherein at least one layer of the laminar structurehas a volume removed to form a cavity; and the cathode slurry wherein atleast an average molecular size of one component of the cathode slurryis reduced in particle size by milling said component; and wherein thecathode slurry is capable of filling the cavity, based on its rheology,while maintaining electroconductivity through the laminar structure inthe cavity; and a circuit electrically connected to a biocompatiblebattery, wherein the circuit provides the controlling voltage signal.23. The method of claim 22 wherein the biomedical device is a contactlens.
 24. A method of manufacturing a cathode slurry mixture for use ina biomedical device comprising the steps of: mixing one or more of aliquid phase pre-mixture with one or more of a solid phase pre-mixtureinto a cathode slurry mixture; obtaining a laminar structure wherein thelaminar structure has a volume removed to form a cavity; filtering thecathode slurry mixture; and distributing the cathode slurry mixture intothe cavity of the laminar structure forming the cathode slurry mixturefor use in a biomedical device; wherein the biomedical device comprises:an insert device comprising: an electroactive element responsive to acontrolling voltage signal; a biocompatible battery; wherein thebiocompatible battery comprises: a first and second electrode; an anode;a separator; and the cavity for storing a cathode mixture; wherein thecathode mixture is capable for storage, based on its rheology, whilemaintaining electroconductivity and biocompatibility; wherein thecathode slurry mixture comprises:  manganese dioxide;  graphite; polyisobutylene (PIB);  Toluene; and wherein at least an averagemolecular size of one component of the cathode mixture is reduced inparticle size by milling said component; and a circuit electricallyconnected to the biocompatible battery wherein the circuit provides thecontrolling voltage signal.